JP2002131915A - Radiation-sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resist composition excellent in resolving power and preservability and having improved edge roughness. SOLUTION: The radiation sensitive resist composition contains (A) a resin containing Si atoms and having a velocity of dissolution in an alkali developing solution increased by the action of an acid, (B) a photo-acid generating agent, (C) a solvent and (D) a compound having a nitrogen-containing basic group and an acidic group in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

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

The above-mentioned chemically amplified resist is suitable for a photoresist for irradiating ultraviolet rays or far ultraviolet rays, but among them, it is necessary to further meet the required characteristics in use. As a photoresist composition for an ArF light source, a resin having an alicyclic hydrocarbon moiety introduced therein for the purpose of imparting dry etching resistance has been proposed. However, such a phenomenon that the development with an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which has been widely used as a resist developing solution in the past, becomes difficult, and the resist is peeled off from the substrate during the development. Can be seen. In response to such a resist hydrophobization, measures such as mixing an organic solvent such as isopropyl alcohol with a developing solution have been studied. Although some results have been obtained, concerns about the swelling of the resist film and the process become complicated. This does not necessarily mean that the problem has been solved. In the approach of improving the resist, many measures have been taken to supplement various hydrophobic alicyclic hydrocarbon sites by introducing a hydrophilic group.

JP-A-10-10739 discloses an energy-sensitive resist containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in the main chain, maleic anhydride, and a monomer having a carboxyl group. Materials are disclosed. JP-A-10-111569 discloses a radiation-sensitive resin composition containing a resin having an alicyclic skeleton in the main chain and a radiation-sensitive acid generator. JP-A-11-109632 describes that a resin containing a polar group-containing alicyclic functional group and an acid-decomposable group is used for a radiation-sensitive material.

As described above, a resin containing an acid-decomposable group used for a photoresist for exposure to far ultraviolet rays generally contains an aliphatic cyclic hydrocarbon group in the molecule at the same time. For this reason, the resin becomes hydrophobic, and there is a problem caused by the hydrophobicity. Various means for improving the above have been studied, but the above techniques still have many insufficient points, and improvements are desired. Further, Japanese Unexamined Patent Publication No.
No. 289340, a negative-type radiation-sensitive resin composition containing a compound having a nitrogen-containing basic group and an acidic group has a developing property, a pattern shape, a focus acceptability, a heat resistance, an adhesive property, a process stability, Attempts have been made to improve resolution, sensitivity, etc.

However, it has been desired to further improve the preservability as well as the resolving power. That is, during storage of the resist solution, there is a problem that particles are generated and performance is deteriorated. Also, improvement in terms of edge roughness has been desired. Edge roughness refers to the fact that the top and bottom edges of a resist line pattern fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. It means that it looks uneven, and in recent years, with the demand for miniaturization of semiconductor chips, the fine semiconductor design pattern is 0.13
Although it reaches a fine region of about 0.35 μm, there is a problem that the resolution of the pattern is hindered by the edge roughness of the line pattern in this region.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a radiation-sensitive resist composition which is excellent in resolution and preservability and has improved edge roughness.

[0009]

Means for Solving the Problems As a result of intensive studies on the constituent materials of the radiation-sensitive resist composition, the present inventors have found that the object of the present invention can be attained by adding a specific nitrogen-containing or acid-containing compound. The present invention has been found to be achieved.
That is, the above object is achieved by the following constitutions.

(1) (A) a resin containing a silicon atom, whose dissolution rate in an alkali developing solution changes due to the action of an acid, (B) a photoacid generator, (C) a solvent, and (D) a molecule containing A radiation-sensitive resist composition comprising a compound having a nitrogen-containing basic group and an acidic group.

(2) The radiation-sensitive resist composition according to the above (1), wherein the acidic group contained in the component (D) is a carboxyl group. (3) The radiation-sensitive resist composition according to the above (1), wherein the acidic group contained in the component (D) is a sulfo group.

(4) The radiation-sensitive resist composition according to the above (1), wherein the acidic group contained in the component (D) is a hydroxyl group. (5) The radiation-sensitive resist composition according to the above (2), which comprises, as the component (D), an alicyclic or aromatic cyclic compound represented by the following general formula (I).

[0013]

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In the formula, R ₁ represents a hydrogen atom or a substituent.
R ₂ represents a substituent. n shows 0-6. n is 2-6
In the case where there are two or more R ₂ , they may be the same or different. X represents an atomic group for forming a 3- to 7-membered alicyclic ring or an aromatic ring, and may have a nitrogen atom, an oxygen atom, a sulfur atom and a polar group, and form a condensed ring. May be. (6) As the component (D), the following general formulas (II) and (II)
The radiation-sensitive resist composition according to the above (2), which comprises the alicyclic compound represented by (I) or (IV).

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In each formula, R ₁ represents a hydrogen atom or a substituent. Two R ₁ in formulas (III) and (IV) may be the same or different. R ₂ represents a substituent. n
Represents 0 to 6. When n is 2 to 6 and a plurality of R ₂ are present, they may be the same or different. X represents an atomic group for constituting a 3- to 7-membered alicyclic ring, and may have a nitrogen atom, an oxygen atom, a sulfur atom and a polar group. Further, a condensed ring may be formed with another alicyclic ring or aromatic ring.

Further, the following embodiments are preferable. (7) As a component (D), a compound having a carboxyl group at a carbon atom other than the α-position of a nitrogen atom forming a nitrogen-containing aromatic ring or a compound having a carboxyl group and an amino group on an aromatic ring is contained. The radiation-sensitive resist composition according to (2), wherein (8) The viscosity at 25 ° C. is 6.0 mPa.s. The radiation-sensitive resist composition according to any one of the above (1) to (7), which is not more than sec. (9) The radiation-sensitive resist composition according to any one of (1) to (8), further comprising (F) a silicon-based and / or fluorine-based surfactant. (10) The above (1) to (9), further comprising (E) a nitrogen-containing basic compound having no acidic group.
The radiation-sensitive resist composition according to any one of the above.

(11) The component (C) is a mixed solvent containing at least one selected from the following solvent group A and at least one selected from the following solvent group B, or at least one selected from group A. The radiation-sensitive resist composition according to any one of the above (1) to (10), which is a mixed solvent containing a seed and at least one selected from the following solvent group C. Group A: propylene glycol monoalkyl ether alkoxylate Group B: propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate Group C: γ-butyrolactone, ethylene carbonate and propylene carbonate

(12) The component (C) contains at least one selected from the following solvent A group, at least one selected from the following solvent B group, and at least one selected from the following solvent C group. The radiation-sensitive resist composition according to any one of the above (1) to (11), comprising a mixed solvent. Group A: propylene glycol monoalkyl ether alkoxylate Group B: propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate Group C: γ-butyrolactone, ethylene carbonate and propylene carbonate (13) The component (C) is an alkyl lactate At least one of them
(1) characterized in that it comprises a mixed solvent characterized by containing a seed, and at least one of an ester solvent and an alkoxyalkyl propionate.
The radiation-sensitive resist composition according to any one of (1) to (12). (14) The radiation-sensitive resist composition according to any one of (1) to (13), wherein the radiation-sensitive resist composition is a positive type.

[0020]

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

[1] As the component (D), any compound can be used as long as it is a compound having a nitrogen-containing basic group and an acidic group in the molecule, and is represented by the following formulas (1) to (5). Compounds having at least one kind of structure and at least one kind of acidic group in the same molecule are preferred. Further, a compound in which the acidic group is a carboxyl group, a sulfo group, or a phenolic hydroxyl group is preferable.

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Here, R ^{40 to} R ⁴³ are the same or different and are an alkyl group having 1 to 6 carbon atoms.

Here, specific examples of the compound having a nitrogen-containing basic group and a carboxyl group in the molecule include amino acids,
Glycine, alanine, valine, leucine, isoleucine, methionine, tryptophan, phenylalanine,
Serine, threonine, cysteine, tyrosine, asparagine, glutamine, ortinine, lysine, histidine,
Arginine, aspartic acid, glutamic acid, hydroxylysine, folic acid, compounds represented by the above formulas (I) to (IV), α of a nitrogen atom forming a nitrogen-containing aromatic ring described later
Compound (V) having a carboxyl group at a carbon atom other than the position (I) and Compound (VI) having a carboxyl group and an amino group on an aromatic ring.

Specific examples of the compound having a nitrogen-containing basic group and a sulfo group in the molecule include thiamine naphthalene disulfonate, thiamine naphthalene lauryl sulfate, and thiamine naphthalene lauryl sulfate.
-Pyridinesulfonic acid and the like. Specific examples of the compound having a nitrogen-containing basic group and a phenolic hydroxyl group in the molecule include 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-amino-p-cresol, and 5-amino- o-cresol, 6-amino-m-cresol, nicotinic acid and the like.

The compound having a nitrogen-containing basic group and an acidic group in the molecule can be used together with a nitrogen-containing basic compound having no acidic group described later. The amount of the compound having a nitrogen-containing basic group and an acidic group in the molecule is as follows:
It is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 0 parts by weight. It is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight. 0.001
If the amount is less than 10 parts by weight, the pattern shape and the adhesiveness tend to be deteriorated.

As the component (D), compounds represented by the above general formulas (I) to (IV) are particularly preferred. R
₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 2 to 10 carbon atoms.
Alkenyl group, an aralkyl group having 7 to 15 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms. These further include a primary aliphatic amino group, Lower aliphatic amino group, hybrid amine substituent, aromatic amine substituent, heterocyclic amine substituent, amide group, imide group, halogen atom, halogen-substituted alkyl group, halogen-substituted aryl group, alkenyloxy group, alkyl It may have a substituent such as an ester group, a heterocyclic group, a hydroxyl group, a carboxyl group, a thiol group, a cyano group, a nitro group, a formyl group, a sulfonyl group, a sulfonamide group, an alkoxy group, an acyl group, and an acyloxy group. . Further, R ₁ and R ₂ each independently represent a primary aliphatic amino group, a secondary aliphatic amino group, a hybrid amine substituent, an aromatic amine substituent, a heterocyclic amine substituent, 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, Represents a sulfonamide group, an alkoxy group, an acyl group, or an acyloxy group. n is preferably from 0 to
4.

The alkyl group as R ₁ and R ₂ preferably has 1 to 20 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, tert-butyl group, pentyl group,
Isopentyl group, tert-amyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group,
Examples thereof include a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, an adamantyl group, a decanyl group, a lauryl group, a palmityl group, and a stearyl group.

The aryl group as R ₁ and R ₂ preferably has 6 to 20 carbon atoms. Specifically, a phenyl group,
Naphthyl group, biphenyl group, phenanthrenyl group, anthranyl group, fluorenyl group, pyrene group and the like, 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
Alkylphenyl groups such as -methylphenyl group, 4-methylphenyl group, ethylphenyl group, 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; dialkylnaphthyl groups such as dimethylnaphthyl group and diethylnaphthyl group; and dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group. The alkenyl group as R ₁ and R ₂ preferably has 2 to 10 carbon atoms, specifically, a vinyl group, an allyl group, a propenyl group, a butenyl group,
Examples thereof include a hexenyl group and a cyclohexenyl group. R
The aralkyl group as ₁ and R ₂ preferably has 7 to 15 carbon atoms, and specific examples include a benzyl group, a phenylethyl group, and a phenethyl group.

Specifically, as the primary aliphatic amine substituent, an amino group, a methylamino group, an ethylamino group,
n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, sec-butylamino group, tert-butylamino group, pentylamino group, tert-amylamino group, cyclopentylamino group, hexylamino group, cyclohexyl Examples include an amino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, cetylamino group, methylenediamino group, ethylenediamino group, and tetraethylenepentaamino group.

The 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 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.

The halogen-substituted aryl group includes fluorobenzene, chlorobenzene, 1,2,3,4,5
-Pentafluorobenzene group and the like. Examples of the alkyloxy group and the alkenyloxy group include a methoxy group,
Ethoxy, propyloxy, isopropyloxy, n-butoxy, sec-butoxy, tert-
Butoxy, pentyloxy, isopentyloxy, tert-amyloxy, hexyloxy, heptyloxy, octyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, norbornyloxy, adamantyloxy Group,
An acryloxy group and a methacryloxy group are exemplified.

Examples of the heterocyclic group include thiophene, furan, tetrahydrofuran, morpholine, pyran, tetrahydropyran, dioxane, thiocarbazole, xanthene group, and thioxanthene group. The alkyl group as R ₁ and R _2, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an acyl group, said R ₁ and R ₂
May have a substituent as a substituent. In this case, a substituent having 12 or less carbon atoms is preferable.

R ₁ may be a double bond between the nitrogen atom to which R ₁ is bonded and an atom adjacent to the nitrogen atom. _Two of R ₂ may together form a substituent having a double bond. The substituent having a double bond in this case is, for example, Ro in -C (= Ro). _Two of R ₂ or R ₁ and R ₂ may together form a ring. Such a ring has 4 carbon atoms.
~ 12 alicyclic and aromatic rings are preferred. The ring further includes R
_A nitrogen atom, an oxygen atom, a sulfur atom, and an unsaturated bond may be contained in the substituent and the ring of ₁ and R ₂ . Particularly preferably, cyclobutane, cyclopentane, cyclohexane,
C4 represented by cycloheptane, benzene ring, naphthalene ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, pyridine ring, piperidine ring, pyrrolidine ring, piperazine ring, morpholine ring, pyridone, pyrrolidone, ε-caprolactam To 7 lactam rings, and 4 to 7 carbon atoms represented by cyclopentanone and cyclohexanone.
And a lactone ring having 4 to 7 carbon atoms, such as γ-butyl lactone and barrel lactone, and a cyclic carbonate.

R ₁ and R ₂ are particularly preferably an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n -Butyl group, sec-butyl group, te
rt-butyl, hexyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, naphthyl, 4-aminophenyl, N, N-
Dimethylaminophenyl group, 4-methoxyphenyl group,
4-hydroxyphenyl group. Further, amide group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiophene ring, furan ring, pyrrole ring, imidazole ring, pyridine ring, piperidine ring, pyrrolidine ring, piperazine ring, morpholine ring, pyrrolidone ring, cyclohexanone ring, γ-butyl lactone ring, hydroxyl group, cyano group, nitro group, formyl group, sulfonyl group, carboxyl group, methoxy group, ethoxy group, tert-butoxy group, benzoyl group, amino group, methylamino group, dimethylamino group are also particularly preferable. .

In the general formula (I), the ring X comprises 3 to
A 7-membered alicyclic ring or an aromatic ring, a 3- to 7-membered alicyclic ring constituted by ring X in formula (II), and a compound represented by formula (II)
The 3- to 7-membered alicyclic ring formed by the ring X in (I) to (IV) may contain a nitrogen atom, an oxygen atom, a sulfur atom and / or a polar group. As the polar group, for example,
-NHCO-, -CONHCO-, -COO-, -OC
_{OO -, - SO 2 -,} - SO 3 -, - SO 2 NH -, - O
-, -NH-, -N <, -CO-. Examples of the 3- to 7-membered alicyclic or aromatic ring constituting the ring X in the general formula (I) include aziridine, azetidine, pyrroline, pyrrolidine, pyrrole, imidazole,
Pyrazoline, pyrazolidine, triazole, oxazole, oxathiazole, thiazole, thiadiazole,
Cyclohexane, piperidine, piperazine, pyridine,
Pyridazine, pyrimidine, pyrazine, triazine, morpholine and the like can be mentioned. Examples of the 3- to 7-membered alicyclic ring constituting the ring X in the general formula (II) include aziridine,
Examples include azetidine, pyrroline, pyrrolidine, pyrazolidine, piperidine, piperazine, and morpholine. 3 to 7 which ring X in formulas (III) to (IV) comprises
As the alicyclic ring of the membered ring, cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene,
Examples include cyclopentadiene, cyclohexane, cyclohexene, dioxane, and the like. Furthermore, aziridine, azetidine, pyrroline, pyrrolidine, pyrazolidine, piperidine, piperazine, morpholine, tetrahydrofuran, tetrahydropyran, dioxane and the like can also be mentioned. These rings may be further condensed to form a polycyclic ring. For example, indole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, carbazole,
Condensed rings such as acridine, phenothiazine, phenanthroline and the like can be mentioned.

Further, as the component (D), a compound (V) having a carboxyl group at a carbon atom other than the α-position of the nitrogen atom forming the nitrogen-containing aromatic ring and a compound having a carboxyl group and an amino group on the aromatic ring Compound (VI) can be mentioned. Examples of the nitrogen-containing aromatic ring of compound (V) include those described above, and preferably include pyridine and pyrrole. The nitrogen-containing aromatic ring may have a substituent. Examples of the substituent include a halogen atom, an alkyl group (preferably having 1 to 5 carbon atoms), a substituted alkyl group (preferably having 1 to 5 carbon atoms), an alkoxy group (preferably having 1 to 5 carbon atoms), a hydroxyl group, a mercapto group, And a nitro group. The carboxyl group may be bonded to a carbon atom of the nitrogen-containing aromatic ring via a linking group. The linking group preferably has 1 to 5 carbon atoms, and examples thereof include a methylene group and an ethynylene group.

Examples of the aromatic ring of the compound (VI) include benzene, naphthalene and the above-mentioned nitrogen-containing aromatic ring, and preferably include benzene, naphthalene and pyrazine. The aromatic ring may have a substituent. Examples of the substituent include a halogen atom, an alkyl group (preferably having 1 to 5 carbon atoms), a substituted alkyl group (preferably having 1 to 5 carbon atoms), an alkoxy group (preferably having 1 to 5 carbon atoms), a hydroxyl group, a mercapto group, And a nitro group. The carboxyl group and the amino group may have a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group (preferably having 1 to 5 carbon atoms), a substituted or unsubstituted phenyl group (preferably having 6 to 10 carbon atoms), a carboxyl group, an amino group, and an amidino group. When the compound has two or more aromatic rings, the carboxyl group and the amino group may be on different aromatic rings.

The following are specific examples I-1 to I-1 represented by the formula (I).
I-53, II-1 to II-1 represented by the formula (II)
9. III-1 to III-2 represented by the formula (III)
7, IV-1 to IV-30 represented by the formula (IV), V-1 to V-23 as the compound (V) and VI-1 to VI-50 as the compound (VI) are exemplified. It is not limited.

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[2] A resin containing a silicon atom (acid-decomposable resin) whose dissolution rate in an alkali developer changes due to the action of an acid of the component (A) is represented by the following general formula (S)
Examples of the resin include a resin containing at least one of the repeating units represented by 1) and the general formula (S2).

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(The above general formula (S1) and general formula (S2)
In the formula, Y represents a group selected from a hydrogen atom, a methyl group, a cyano group and a chlorine atom, and L represents a hydrogen atom or -C
A group represented by OXAR (X is O, S, -NH
-, or -NHSO ₂ -) shows a. A represents a single bond or a divalent linking group. R represents a hydrogen atom, a cyano group, a hydroxyl _{group, -COOH, -COOR 6, -CO-} NH-R 7, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkoxy group. R ₇ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

L ₁ and L ₂ each independently represent a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, and a nitrogen atom (N) and an oxygen atom (O) It may intervene. R ₃ and R ₄ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms.
Note that R ₃ and R ₄ may be linked by an alkylene chain to form a cyclic structure. R ₅ represents an alkyl group having a straight-chain or branched having 1 to 10 carbon atoms, a phenyl group, a trialkylsilyl group, a trialkylsilyl group. p is 1-3
Is shown. )

Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Can be The above carbon number 1
Examples of the alkylene group of 10 include a methylene group, an ethylene group, and a propylene group. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group. Can be mentioned.

Further, further substituents of the above-mentioned alkyl group, alkylene group and alkoxy group include those having 1 to 4 carbon atoms.
And an alkoxy group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

As described above, as the acid-decomposable resin, a resin containing Si in the side chain is exemplified, but a resin containing Si in the main chain of the resin may be used. For example, a resin having a siloxane skeleton is exemplified. it can. Among them, a polysiloxane in which a group capable of decomposing under the action of an acid to increase the dissolution rate of a resin in an alkali developing solution (also referred to as an acid-decomposable group) is preferably linked to Si of a siloxane skeleton via a cyclohexyl group. it can. Acid-decomposable resins, in addition to the above, various for the purpose of adjusting dry etching resistance and standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc., which are general requirements for resists It can be used as a copolymer with a monomer repeating unit.

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

Specifically, for example, acrylic esters such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl acrylate, etc.);

Methacrylic esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl Group, cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Cyclohexyl group, etc.), N-hydroxyethyl-N-methylacrylamide, N-2-
Acetamidoethyl-N-acetylacrylamide and the like;

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

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like;

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of fumaric acid (eg, dibutyl fumarate, etc.) or monoalkyl esters; other acrylic acid, methacrylic acid, croton Acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile,
Examples thereof include methacrylonitrile and maleilenitrile. In addition, any addition-polymerizable unsaturated compound copolymerizable with the above various repeating units may be used.

In the acid-decomposable resin, the molar ratio of each repeating unit structure is determined by the acid value, the resistance to dry etching of the resist, the suitability for a standard developing solution, the substrate adhesion, the dependency of the resist profile on the density of the resist, and the general properties of the resist. Are appropriately set in order to adjust the resolution, heat resistance, sensitivity, and the like required for the above.

The content of the repeating unit having a partial structure represented by the general formula (S1) and / or (S2) in the acid-decomposable resin is 10 to 85 mol%, preferably 20 to 20 mol%, of all the repeating units. ~ 80 mol%, more preferably 30
~ 75 mol%.

The weight-average molecular weight Mw of the acid-decomposable resin is preferably from 1,000 to 1,000, as determined by gel permeation chromatography, based on polystyrene standards.
000, more preferably 1,500 to 500,000,
It is more preferably in the range of 2,000 to 200,000, and particularly preferably in the range of 2,500 to 100,000. As the weight average molecular weight increases, heat resistance and the like improve, while developability and the like decrease. It is adjusted to a preferable range by the balance of. The acid-decomposable resin used in the present invention can be synthesized according to a conventional method. That is, when an acid-decomposable resin containing Si in the side chain is used, for example, a vinyl monomer having Si in the side chain can be synthesized by a radical polymerization method. When an acid-decomposable resin containing Si in the main chain is used, it can be synthesized, for example, by linking an acid-decomposable group to polysiloxane.

In the radiation-sensitive resist composition of the present invention, the addition amount of the acid-decomposable resin in the whole composition is preferably 40 to 99.9% by weight, more preferably 50 to 99. 7% by weight.

[3] Next, a compound (photoacid generator) which generates an acid upon irradiation with actinic rays or radiation, which is 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 (400 to
200 nm ultraviolet light, far ultraviolet light, particularly preferably g
Line, h line, i line, KrF excimer laser light), ArF
Excimer laser light, F ₂ excimer laser light, an electron beam, an X-ray, a compound generating an acid by a molecular beam or an ion beam, and a mixture thereof can be appropriately selected and used.

Other photoacid generators used in the present invention include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts;
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 which 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.

One of the photoacid generators 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, where y is 0 to
A fluorine-substituted linear alkyl group, which is an integer of 9;

The cation moiety of the photoacid generator is preferably represented by the following formulas (A1-I) to (A1-III).

[0081]

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The above general formulas (A1-I) to (A1-III)
In the formula, R _{1 to} R ₃₇ may be 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 or aryl group. Two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , and R _{28 to} R ₃₇ are bonded to form one or two or more selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom.
A ring containing more than one species may be formed.

As the linear or branched alkyl group for R _{1 to} R ₃₈ , a methyl group, an ethyl group, an optionally substituted
Examples thereof include those having 1 to 4 carbon atoms such as a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. 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 represented by R _{1 to} R ₃₇ include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. Such a C1-C4 thing is mentioned. 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. As the aryl group for R ₃₈ , for example, a C 6 carbon atom which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group
To 14 items. As these substituents, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, an iodine atom) and a carbon atom having a carbon number of 6 to 1 are preferable.
Examples thereof include zero aryl groups, alkenyl groups having 2 to 6 carbon atoms, cyano groups, hydroxy groups, carboxy groups, alkoxycarbonyl groups, and nitro groups. Also, R _1-
Among R ₁₅ , R _{16 to} R ₂₇ , and R _{28 to} R ₃₇ , one or more selected from a single bond, carbon, oxygen, sulfur, and nitrogen, formed by combining two or more of them Examples of the ring 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 (A1-6) of the photoacid generators represented by formulas (A1-I) to (A1-III)
4) is shown below.

[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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Further, the following photoacid generators can 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).

[0094]

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

[0096]

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

[0098]

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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, B
F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , Cl
Condensed polynuclear aromatic sulfonic acid anions such as perfluoroalkanesulfonic acid anions such as O ₄ ⁻ and CF ₃ SO ₃ ⁻ , pentafluorobenzenesulfonic acid anion, naphthalene-1-sulfonic acid anion, anthraquinonesulfonic acid anion and sulfonic acid group Dyes and the like may be included, but are not limited thereto.

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

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

[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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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).

[0112]

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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.

[0114]

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[0115]

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[0116]

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

[0118]

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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.

[0120]

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The amount of the photoacid generator to be added is usually 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 solid content 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.

[4] The solvent (C) will be described. Examples of the solvent that the radiation-sensitive resist composition of the present invention contains as component (C) include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. Propionate,
Propylene glycol monoethyl ether acetate,
Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 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 resist composition of the present invention, the applicability to a substrate, the 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, whereby a radiation-sensitive resist composition having particularly excellent particle reduction properties can be obtained. 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.

Further, 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 present invention, the radiation-sensitive resin composition having the above-mentioned components has a viscosity at 25 ° C. of not more than 6.0 mPa · sec, preferably from 0.9 to 5.0.
mPa · sec, more preferably 1.5 to 4.5 mPa
・ It is good to be within the range of sec. The viscosity is 6.0mPa.
If the time exceeds sec, the resolution performance deteriorates, which is not preferable. The viscosity at 25 ° C. is, for example, 25 ° C.
, And then can be measured with an E-type viscometer or the like.

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, but the above ratio can be appropriately changed depending on the kind and amount of the above-mentioned optional components. 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.

[5] The resist composition of the present invention preferably contains a nitrogen-containing basic compound having no acidic group as component (E). This has the effect of improving edge roughness.

The preferred organic basic compound having no acidic group which can be used in the present invention is a compound which is more basic than phenol. The acidic group that the organic basic compound does not have is a phenolic hydroxyl group, a sulfonic acid group,
There is a phosphate group. In particular, a nitrogen-containing basic compound having no acidic group is preferable, and examples thereof include compounds having the following structures.

[0131]

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Here, R²⁵⁰, R²⁵¹And R²⁵²Are each
Independently, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
1-6 aminoalkyl groups, hydroxy having 1-6 carbon atoms
Alkyl group or substituted or unsubstituted 6 to 20 carbon atoms
An aryl group, where R ²⁵¹And R²⁵²Are connected to each other
To form a ring.

[0133]

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(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ independently represents an alkyl group having 1 to 6 carbon atoms)

Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound 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 aminoalkylmorpholine and the like can be mentioned. 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 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, hexamethylenetetramine,
CHMETU, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate is preferred.

These basic compounds having no acidic group may be used alone or in combination of two or more.
The amount used is usually from 0.001 to 10% by weight, preferably from 0.0 to 10% by weight, based on the solid content of the entire photosensitive resin composition.
1 to 5% by weight. If the amount is less than 0.001% by weight, the effect of the addition of the basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

[6] The resist composition of the present invention may contain any one of component (F) a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom, or Preferably, it contains more than one species.
This is effective for improving storage stability, particularly for reducing the initial value of particles.

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 compounding 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.

[7] Other Components The resist composition of the present invention may further contain, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, and a compound which promotes solubility in a developer. Etc. can be contained.

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 wavelength 19 of the composition is used.
The transmittance for light of 3 nm can be adjusted by the type, copolymerization ratio and molecular weight of each repeating unit in the component (A). Further, the solubility of the component (B), the acid-decomposable dissolution inhibiting compound, the dye, the plasticizer, the surfactant, the photosensitizer, the organic base compound, and the developer in the exposed portion, which have absorption at the wavelength, is determined. This is achieved by appropriately adjusting the amount of the compound to be promoted.

In the present invention, if necessary, a commercially available inorganic or organic antireflection film can be used. As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, and an organic film type made of a light absorbing agent and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. Examples of the organic antireflection film include a film composed of a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin, and a light absorbing agent, and a maleic anhydride copolymer described in US Pat. No. 5,294,680. Reaction product of coalescing and diamine type light absorbing agent
JP-A-6-1186, containing a resin binder described in JP-A-118631, and a methylolmelamine-based thermal crosslinking agent.
No. 56, an acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule;
87115 and those comprising a methylol melamine and a benzophenone-based light absorbing agent, and those described in JP-A-8-179509 in which a low molecular weight light absorbing agent is added to a polyvinyl alcohol resin. Also, as an organic anti-reflection film,
DUV30 series manufactured by Brewer Science,
DUV-40 series, Shipley's AC-2, AC
-3 can also be used.

The resist solution is applied onto a substrate (eg, a silicon / silicon dioxide coating) used for the manufacture of 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.

[0147]

(Synthesis of acid-decomposable resin)

Synthesis of Polym.1 60g of maleic anhydride, allyltrimethylsilane 70
g, t-butyl acrylate 60 g, methyl acrylate 14 g in dry tetrahydrofuran (THF) 200 m
Then, the mixture was heated to 65 ° C. under a nitrogen stream. When the reaction temperature was stabilized, an initiator V-59 manufactured by Wako Pure Chemical Industries, Ltd. was added at 10 mol% of the total number of moles of the monomer to start the reaction. After reacting for 20 hours, the reaction mixture was diluted with THF for 2 hours.
After diluting it twice, it was poured into a large amount of hexane to precipitate a white powder. Next, in order to reduce residual monomers and low molecular components, the polymer obtained by dissolving the precipitated powder in acetone was washed with hexane / acetone (8/2) and dried to synthesize Polym.1 having the following composition. did. As a result of GPC measurement, the molecular weight of the obtained Polym.1 was 5600 in weight average using polystyrene as a standard sample, and the content of components having a molecular weight of 1,000 or less was 4% by area ratio of GPC. Resins (Polyms. 2 to 11) having the following composition and weight average molecular weight were synthesized in the same manner as in the above Synthesis Examples.

[0148]

Embedded image

[0149]

Embedded image

[0150]

Embedded image

Examples 1 to 18 and Comparative Examples 1 to 7 [Preparation of radiation-sensitive resist composition] Acid-decomposable resin 1.37 g Photoacid generator 30 mg Basic compound 1.5 mg (D) Compound 3.0 mg required Was mixed with 30 mg of a solvent shown in Table 2 and dissolved in 6.0 g of a solvent shown in Table 2. The obtained solution was filtered through a 0.1 μm microfilter to prepare radiation-sensitive resin compositions of Examples 1 to 18 having the compositions shown in Table 1. Also in Comparative Examples 1 to 7, radiation-sensitive resin compositions were prepared in the same manner as in Examples 1 to 18. The resins A, B, C, and D used in Comparative Examples 1 to 4 were used.
Is the following resin. Resin A: poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] (weight average molecular weight 2000
0, dispersity 1.90) Resin B: poly [p- (tert-butoxystyrene / p)
-Hydroxystyrene] (weight average molecular weight 15,000,
Resin C: poly [p- (tert-butoxycarbonyloxystyrene / p-hydroxystyrene) (weight average molecular weight 10,000, dispersity 1.50) Resin D: poly [p- (1-ethoxyethoxy) ) Styrene / p-hydroxystyrene / p- (tert-butoxystyrene) (weight average molecular weight 15,000, dispersity 1.8)
5)

[0152]

[Table 1]

The 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

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 In Table 1, the ratio of a plurality of components used is a weight ratio.

(Evaluation Test) The resist solution prepared above was applied to a DUV30 (1600) manufactured by Brewer Company 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 exposed to an ArF excimer laser stepper while loading a resolving power mask thereon while changing the exposure amount and focus. Then 125 in the clean room
After heating at 90 ° C. for 90 seconds, the film was developed with a tetramethylammonium hydroxide developer (2.38% by weight) for 60 seconds and rinsed with distilled water to obtain a pattern. The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope, and the resist was evaluated as follows. Table 2 shows the evaluation results.

[Resolution]: First, the sensitivity (Eth) was determined. Next, a 0.15 μm line and space of 1: 1
And the minimum line width of the separated line and space at this exposure amount was taken as the resolution of the evaluation resist.

[Edge Roughness]: The edge roughness was measured using a lateral scanning electron microscope (SEM).
15 μm line and pace (line: space =
1: 1) The edge roughness of the pattern is used, the line pattern edge is detected at a plurality of positions in the measurement monitor, and the variance (3σ) of the variation of the detected position is used as an index of the edge roughness. The smaller the value, the better.

[Number of Particles and Increase in Number of Particles after Preservation with Time]: Immediately after preparation of the radiation-sensitive resist composition solution (coating solution) prepared as described above (initial value of particles) and at 4 ° C. Particles in the liquid after standing for a week (the number of particles after aging) are manufactured by Rion,
It was counted by a particle counter. Along with the particle initial value, the number of particles increased by (number of particles after aging) − (particle initial value) was evaluated. Table 2 shows the results.

[0160]

[Table 2]

As shown in Table 2, the radiation-sensitive resist composition of the present invention showed excellent performance in all evaluation items.

[0162]

According to the present invention, it is possible to provide a radiation-sensitive resin composition having a high resolving power and improved edge roughness and storage stability in the production of semiconductor devices.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/075 511 G03F 7/075 511 H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA01 AA02 AA03 AA04 AA10 AA14 AB16 AC08 AD03 BE00 BE10 BG00 CB33 CB34 CC03 CC20 4J002 BE041 BG071 BH001 BJ001 BQ001 CP031 EB006 EN027 EN107 EN117 EN136 EQ016 ES006 ES007 EU017 EU027 EU047 EU057 EU077 EV117 EV217 EV137 EV137 EV147 EW176 EY006 EZ006 FD206 GP03

Claims (6)

[Claims] (1) a resin containing a silicon atom, (B) a photoacid generator, (C) a solvent, and (D) a molecule containing (A) a dissolving rate in an alkali developing solution which is changed by the action of an acid. A radiation-sensitive resist composition comprising a compound having a nitrogen-containing basic group and an acidic group. 2. The radiation-sensitive resist composition according to claim 1, wherein the acidic group contained in the component (D) is a carboxyl group. 3. The radiation-sensitive resist composition according to claim 1, wherein the acidic group contained in the component (D) is a sulfo group. 4. The radiation-sensitive resist composition according to claim 1, wherein the acidic group contained in the component (D) is a hydroxyl group. 5. The radiation-sensitive resist composition according to claim 2, wherein the component (D) comprises an alicyclic or aromatic compound represented by the following general formula (I). . Embedded image In the formula, R ₁ represents a hydrogen atom or a substituent. R ₂ represents a substituent. n shows 0-6. When n is 2 to 6 and R ₂ is two or more, they may be the same or different. X represents an atomic group for forming a 3- to 7-membered alicyclic ring or an aromatic ring, and may have a nitrogen atom, an oxygen atom, a sulfur atom and a polar group, and form a condensed ring. May be. 6. A compound represented by the following general formula (II):
3. The radiation-sensitive resist composition according to claim 2, comprising an alicyclic compound represented by (III) or (IV). Embedded image In each formula, R ₁ represents a hydrogen atom or a substituent. Two R ₁ in formulas (III) and (IV) may be the same or different. R ₂ represents a substituent, and n represents 0 to 6. When n is 2 to 6 and a plurality of R ₂ are present, they may be the same or different. X represents an atomic group for constituting a 3- to 7-membered alicyclic ring, and includes a nitrogen atom, an oxygen atom,
It may have a sulfur atom and a polar group. Further, a condensed ring may be formed with another alicyclic ring or aromatic ring.