JP2002131916A - Radiation-sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resist composition having superior resolving power and preservability and a radiation sensitive resist composition further having improved edge roughness. SOLUTION: Each of the radiation sensitive resist compositions contains a resin having a velocity of dissolution in an alkali developing solution increased by the action of an acid, a photo-acid generating agent, a solvent and a specified alicyclic or aromatic compound.

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.

[0007] Further, it has been desired to improve the storage stability as well as the resolving power of the conventional compositions. That is, particles are generated during storage of the resist solution,
There was a problem that performance 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 design pattern of the fine semiconductor has reached a fine region of 0.13 to 0.35 μm. There is a problem that the resolution of the pattern is hindered by the edge roughness.

[0008]

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

[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 whose dissolution rate in an alkali developer changes by the action of an acid, (B) a photoacid generator, (C) a solvent, and (D) a compound represented by the following general formula (1): A radiation-sensitive resist composition comprising an alicyclic or aromatic cyclic compound.

[0011]

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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 containing at least one structure connected with a nitrogen atom and one carbonyl carbon atom interposed therebetween; It may have an atom, a sulfur atom and a polar group, and may form a condensed ring.

(2) (A) a resin whose dissolution rate in an alkali developing solution is changed by the action of an acid, (B) a photoacid generator, (C) a solvent, and (D) the following general formula (2): 3),
Or a radiation-sensitive resist composition comprising the alicyclic compound represented by (4).

[0014]

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In each formula, R ₁ represents a hydrogen atom or a substituent. Two R ₁ in formulas (3) and (4) 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 contains at least one structure in which a nitrogen atom and a carbonyl carbon atom are connected to each other by sandwiching one carbon atom in the general formula (3). In the general formulas (2) and (4), X is a bond connected to two carbon atoms. The atomic group for constituting a 3- to 7-membered alicyclic ring. However, the ring may have a nitrogen atom, an oxygen atom, a sulfur atom and a polar group, and may form a condensed ring with an alicyclic group or an aromatic ring group.

(3) The viscosity at 25 ° C. is 6.0 mPa.s. s
ec or less, the radiation-sensitive resist composition according to (1) or (2), (4) The radiation-sensitive resist composition according to any one of (1) to (3), further comprising (E) a nitrogen-containing basic compound having no acidic group. (5) The radiation-sensitive resist composition according to any one of (1) to (4), further comprising (F) a fluorine-based and / or silicon-based surfactant.

Further, preferred embodiments include the following. (6) Component (C) is at least one selected from the following solvent A group and at least one selected from the following solvent B group
A mixed solvent containing at least one selected from the group of solvents A and at least one selected from the group of the following solvents C (1) The radiation-sensitive resist composition according to any one of (1) to (5). 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

(7) The component (C) contains at least one selected from the group of solvents A, at least one selected from the group of solvents B, and at least one selected from the group of solvents C. The radiation-sensitive resist composition according to any one of (1) to (5), comprising a mixed solvent.

(8) The component (C) contains a mixed solvent characterized by containing at least one kind of alkyl lactate and at least one kind of ester solvent and alkoxyalkyl propionate. The radiation-sensitive resist composition according to any one of (1) to (5), wherein (9) The radiation-sensitive resist composition according to any one of (1) to (8), 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] First, the general formulas (1) to (D) of the component (D)
The compound represented by (4) will be described. R ₁ and R ₂
As each independently an alkyl group having 1 to 20 carbon atoms;
An aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, and 1 to 2 carbon atoms
And alkoxy groups having 0 to 2 carbon atoms, and acyl groups having 2 to 20 carbon atoms. These further include a primary aliphatic amino group, a secondary aliphatic amino group, a hybrid amine substituent, and an aromatic amine substituent. Group, heterocyclic amine substituent, 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. Further, R ₁ and R ₂
As each independently a primary aliphatic amino group, a secondary aliphatic amino group, a hybrid amines substituent, an aromatic amines substituent, a heterocyclic amines substituent, an amide group, an 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 0-4.

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 partimyl 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.

Primary aliphatic amine substituents include amino, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino and sec-butylamino. , 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.

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.

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.

The alkyl group as R ₁ and R _2, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an acyl group may have a group mentioned as R ₁ and R ₂ in the above 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 (1), 3 to 3 constituting the ring X
7-membered alicyclic ring or aromatic ring, 3- to 7-membered alicyclic ring constituted by ring X in general formula (2), general formula (3) to
The 3- to 7-membered alicyclic ring constituted by the ring X in (4) may contain a nitrogen atom, an oxygen atom, a sulfur atom and / or a polar group. As the polar group, for example, -NH
CO-, -CONHCO-, -COO-, -OCOO
_{-, - SO 2 -, -} SO 3 -, - SO 2 NH -, - O-,
—NH—, —N <, and —CO— can be exemplified.

In the general formula (1), 3 to 3 constituting the ring X
As a 7-membered alicyclic ring or aromatic ring, 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. Examples of the 3- to 7-membered alicyclic ring constituting the ring X in the general formula (2) include aziridine, azetidine, pyrroline, pyrrolidine, pyrazolidine, piperidine, piperazine, and morpholine. The ring X in the general formulas (3) to (4) is 3 to
Examples of the 7-membered alicyclic ring include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, 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, fused rings of indole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, carbazole, acridine, phenothiazine, phenanthroline and the like can be mentioned.

Specific examples 1-1 to 1 represented by the following formula (1)
1-54, 2-1 to 2-19 represented by the formula (2), 3-1 to 3-27 represented by the formula (3), 4-1 to 4-4 represented by the formula (4) Although 30 is illustrated, it is not limited to these.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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The amount of the component (D) used is the amount of the resin 10
It is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 0 parts by weight. If the amount is less than 0.001 part by weight, the pattern shape and the adhesiveness tend to deteriorate, while if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the radiation irradiated part tends to deteriorate.

[2] As the resin as the component (A), known resins can be used as long as the resin dissolves in an alkali developing solution under the action of an acid (also referred to as "acid-decomposable resin"). As the preferable resin of the component (A),
i) at least one repeating structural unit selected from the group of repeating structural units represented by the following general formulas (Ia) and (Ib), a repeating structural unit represented by the following general formula (II), and ( ii) There is a resin having a group that is decomposed by the action of an acid and having an increased dissolution rate in an alkaline developer by the action of an acid.

[0049]

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

[0051]

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(In the —Y group, R _{21 to} R ₃₀ are each independently
Represents a hydrogen atom or an alkyl group which may have a substituent. a and b represent 1 or 2. ) In the formula (Ib): Z
_2, -O- or -N (R ₃₎ - represents a. Where R ₃ is
Hydrogen atom, a hydroxyl group or -OSO ₂ -R _4. R ₄ is
Represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue. In the formula (II), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent. Z is linked 2
Represents an atomic group for forming an alicyclic structure which may have a substituent and contains two carbon atoms (CC).

(2) In the general formula (II), Z is
It is preferable to represent an atomic group for forming a bridged alicyclic structure which contains two bonded carbon atoms (CC) and may have a substituent. (3) Further, the above general formula (II) is represented by the following general formula (II-
A) or the general formula (II-B) is preferred.

[0054]

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In the formulas (II-A) and (II-B): R _{13 to} R ₁₆
Is independently a hydrogen atom, a halogen atom, a cyano group,
—COOH, —COOR ₅ (R ₅ is as defined above), a group decomposed by the action of an acid, —C (＝ O) —X
-AR ₁₇ , or an alkyl group or a cyclic hydrocarbon group which may have a substituent. Further, at least two members out of R _{13 to} R ₁₆ may combine to form a ring. n represents 0 or 1. Here, X and A are as defined above. R ₁₇ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an optionally substituted alkoxy group, —CO
—NH—R ₆ , —CO—NH—SO ₂ —R ₆ (R ₅ , R
₆ each has the same meaning as described above) or the above-mentioned -Y group.

(4) The resin of the above (A) is subjected to a polymerization reaction by heating a solution containing a monomer corresponding to a repeating structural unit constituting the resin and a radical initiator, and then further reacting a radical. It is preferably a polymer obtained by adding the agent, heating and performing the polymerization reaction again. (5) The resin of the above (A) is used to prepare a polymerization reaction solution after completion of the polymerization reaction by using water, alcohols, ethers, ketones, amides, esters and lactones, nitriles, hydrocarbons, and the like. It is preferable that the polymer is collected in the form of a powder after being charged into at least one solvent selected from a solvent group consisting of a mixed solvent of the above to precipitate the polymer.

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

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

The above R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₂₁
As the alkyl group for R _{30 to} R _{30, a} linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. Represents a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples of the cyclic hydrocarbon group for R ₁ , R ₂ , R ₅ , and R ₆ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a norbornyl group, a boronyl group, and an isobornyl group. ,
Examples include a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. Examples of the alkoxy group in R ₁ and R ₂ include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. 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.

Further substituents of the above-mentioned alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

The divalent linking group of A in the above formulas (Ia) and (Ib) includes an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group,
Examples thereof include a single group selected from the group consisting of an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups. Examples of the alkylene group and substituted alkylene group in A include groups represented by the following formula. -[C (R ₂ ) (R _b )] r- wherein R ₂ and R _b represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

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

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

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[0071]

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In the general formula (II), R ₁₁ , R
Each ₁₂ independently represents a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent.
Z represents an atomic group containing two bonded carbon atoms (C-C) and forming an alicyclic structure which may have a substituent.

Examples of the halogen atom for R ₁₁ and R ₁₂ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. The alkyl group for R ₁₁ and R ₁₂ is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms. More preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group.

Further substituents in the alkyl groups of R ₁₁ and R ₁₂ include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom, and examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. And formyl group as acyl group,
An acetyl group and the like can be mentioned, and an acyloxy group can be an acetoxy group and the like.

The atomic group for forming the alicyclic structure of Z is an atomic group for forming a repeating structural unit of an alicyclic hydrocarbon which may have a substituent on the resin. An atomic group for forming a bridged alicyclic structure forming a repeating structural unit of an alicyclic hydrocarbon of the formula is preferred. Examples of the skeleton of the formed alicyclic hydrocarbon include those represented by the following structures.

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Preferable bridged alicyclic hydrocarbon skeletons include (5), (6), (7),
(9), (10), (13), (14), (15),
(23), (28), (36), (37), (42),
(47). The alicyclic hydrocarbon skeleton may have a substituent. As such a substituent, R _{13 in the} above general formula (II-A) or (II-B)
It can be mentioned ~R _16. Among the repeating structural units having a bridged alicyclic hydrocarbon, the repeating structural units represented by the general formula (II-A) or (II-B) are more preferable. In the formula (II-A) or (II-B), R _{13 to} R ₁₆ each independently represent a hydrogen atom, a halogen atom, a cyano group, —COOH, or —COO.
R ₅ (R ₅ is an alkyl group which may have a substituent,
A cyclic hydrocarbon group or the same -Y group as in the above formula (I)), a group decomposed by the action of an acid, -C (=
O) —X—A—R ₁₇ , or an alkyl group or a cyclic hydrocarbon group which may have a substituent. n is 0 or 1
Represents X is an oxygen atom, a sulfur atom, -NH-, -NH
Represents SO ₂ — or —NHSO ₂ NH—. R ₁₇ is -C
OOH, -COOR _5, -CN, hydroxyl, optionally substituted alkoxy _{group, -CO-NH-R 6,} -C
_{O-NH-SO 2 -R 6} (R 5, R 6 has the same meaning as defined above) represents a -Y group or the general formula (Ia). A represents a single bond or a divalent linking group.

In the acid-decomposable resin used in the present invention, the acid-decomposable group has the above-mentioned —C (＝ O) —XA—R ₁ ,
It may be contained in —C (−O) —XA—R ₂ or as a substituent of Z in the general formula (II). The structure of the acid-decomposable group is represented by —C (＝ O) —X ₁ —R ₀ . In the formula, R ₀ represents a tertiary alkyl group such as t-butyl group, t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy 1-alkoxyethyl group such as ethyl group, 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- Examples thereof include an oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue, and a 2- (γ-butyrolactonyloxycarbonyl) -2-propyl group. X ₁ has the same meaning as X described above.

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

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

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

As the alkoxy group for R ₁₇ ,
Examples thereof include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Examples of further substituents in the above-mentioned alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. As the halogen atom, a chlorine atom, a bromine atom, a fluorine atom,
And iodine atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

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

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

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

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

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[0101]

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The acid-decomposable resin used in the present invention comprises at least one of the repeating structural units represented by the general formulas (Ia) and (Ib), and the compound represented by the general formula (II)
(Including one or more types of repeating structural units represented by the general formulas (II-A) and (II-B)), dry etching resistance, suitability for a standard developer, and substrate adhesion For the purpose of adjusting the properties, the resist profile, and the resolution, heat resistance, sensitivity, and the like, which are general requirements of the resist, a copolymer containing repeating structural units of various monomers can be used. Preferred copolymerization components include repeating structural units represented by the following general formulas (IV ') and (V').

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Here, in the formula, Z is an oxygen atom, -NH-,-
_{N (-R 50) -, -} N (-OSO 2 R 50) - represents, R
₅₀ also has the same meaning as the above (substituted) alkyl group and (substituted) cyclic hydrocarbon group. The above general formulas (IV ') and (V')
Specific examples of the repeating structural unit represented by the following [IV '
-9] to [IV'-16], [V'-9] to [V'-16]
However, the present invention is not limited to these specific examples.

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The acid-decomposable resin used in the present invention may further be copolymerized as long as the effects of the present invention are effectively obtained, provided that the following monomers give the repeating structural units constituting the resin. Although it may be, it is not limited to the following monomers. Thereby, the performance required for the resin, in particular, (1) solubility in a coating solvent, (2)
Film-forming properties (glass transition point), (3) alkali developability,
(4) membrane loss (hydrophilic / hydrophobic, alkali-soluble group selection),
Fine adjustment of (5) adhesion of the unexposed portion to the substrate and (6) dry etching resistance can be performed.

Examples of such a comonomer include acrylates, methacrylates, and the like.
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

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

Methacrylic acid esters, 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, cycloethyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide and the like;

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

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

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

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

In the acid-decomposable resin used in the present invention, the repeating structural unit represented by the general formula (Ia) and / or the general formula (Ib) and the general formula (II) (the general formula (II)
-A), the content of the repeating structural unit represented by the general formula (II-B) is as follows: the desired dry etching resistance of the resist, sensitivity, prevention of pattern cracking, substrate adhesion, resist profile, and It can be set as appropriate in consideration of the resolving power, heat resistance, and the like, which are necessary requirements of general resists. Generally, the acid-decomposable resin used in the present invention contains a repeating structural unit represented by the general formula (Ia) and / or (Ib) and a repeating structural unit represented by the general formula (II) The amount is
The amount is suitably at least 25 mol%, preferably at least 30 mol%, more preferably at least 35 mol%, in all the monomer repeating structural units of the resin.

Further, in the acid-decomposable resin used in the present invention, the content of the repeating structural unit (general formula (IV ′) or general formula (V ′)) derived from the above-mentioned preferable comonomer in the resin is preferred. The amount can also be appropriately set according to the desired performance of the resist, but is generally represented by the repeating structural unit represented by the general formula (Ia) and / or the general formula (Ib) and the general formula (II). 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. Further, the content of the repeating structural unit based on the monomer of the further copolymerization component in the resin can be appropriately set according to the desired performance of the resist, but generally, the general formula (Ia) And / or a repeating structural unit represented by the general formula (Ib);
It is preferably 99 mol% or less, more preferably 90 mol%, based on the total number of moles of the repeating structural units represented by I).
Mol% or less, more preferably 80 mol% or less.
If the amount of the repeating structural unit based on the monomer of the further copolymer component exceeds 99 mol%, the effect of the present invention is not sufficiently exhibited, which is not preferable.

In the acid-decomposable resin used in the present invention, the group decomposed by the action of an acid is represented by the general formula (I)
a) and / or a repeating structural unit represented by the general formula (Ib), a repeating structural unit represented by the general formula (II), or a repeating structural unit based on a monomer of a copolymer component. The content of the repeating structural unit containing a group that is decomposed by the action of an acid is suitably 8 to 60 mol%, preferably 10 to 55 mol%, of all the repeating structural units in the resin. More preferably, 12
~ 50 mol%.

The acid-decomposable resin used in the present invention comprises a monomer corresponding to the repeating structural unit represented by the general formula (II) and maleic anhydride, and when a copolymerization component is used, the copolymerization component The monomers are copolymerized and copolymerized in the presence of a polymerization catalyst, and the repeating structural units derived from maleic anhydride in the obtained copolymer are subjected to ring-opening esterification with alcohols under basic or acidic conditions. Alternatively, it can be synthesized by a method of hydrolyzing and then converting the carboxylic acid moiety generated thereafter to a desired substituent.

The above-mentioned copolymerization (hereinafter, also simply referred to as “polymerization”) can be carried out according to a conventional method (for example, by radical polymerization). The following methods can be mentioned.

The monomer to be reacted is dissolved in a reaction solvent or made uniform without a solvent, heated and stirred under a nitrogen atmosphere to a desired temperature, and then a radical initiator is added in a lump or in a batch. A solution in which a monomer to be reacted is dissolved in a reaction solvent together with an initiator, and this is heated to a desired temperature under a nitrogen atmosphere, or a part of the reaction solvent or the monomer is dissolved in the reaction solvent. For example, a dropping method in which the solution is gradually dropped may be used.

Preferred are the split addition method and the dropping method of the initiator. By selecting this method, the resist performance, including the resolution and edge roughness, which are the effects of the present invention, although the details are completely unknown, are improved.

The reaction temperature can be appropriately set depending on the type of the initiator, but is generally from 30 ° C. to 180 ° C. Preferably 4
0 ° C to 160 ° C, more preferably 50 ° C to 14 ° C.
0 ° C.

In the case of the split addition method, the interval between additions of the initiator is 5 minutes to 6 hours, preferably 10 minutes to 5 hours.
More preferably, it is 15 minutes to 4 hours. The dropping time when the dropping method is employed can be variously set depending on the reaction temperature, the type of the initiator, and the monomer to be reacted.
Time. It is preferably 45 minutes to 6 hours, more preferably 1 hour to 5 hours.

In the case of the batch method or the split addition method, after completion of the addition of the initiator, the mixture is heated and stirred at a desired temperature under a nitrogen atmosphere for a certain period of time. Also in the case of the dropping method, after completion of the dropping, the mixture is heated and stirred at a desired temperature for a certain period of time in a nitrogen atmosphere. The heating time varies depending on the reaction temperature and the type of the initiator, but is generally within 24 hours. It is preferably within 20 hours, more preferably within 18 hours.

In any case, it is preferable to continue the heating and stirring for a certain period of time and then add the initiator again.
By adding an initiator, the details are unknown, but as a result, the sensitivity and the resolving power are improved. After the addition of the initiator, the mixture is heated and stirred for a certain period of time. After the addition of the initiator, the reaction temperature may be increased.

As the solvent used in the reaction, any solvent can be used as long as it does not dissolve the monomer species used and inhibits polymerization (inhibition of polymerization, for example, nitrobenzenes, chain transfer, for example, mercapto compounds). Examples thereof include alcohols, ethers, ketones, amides, esters and lactones, nitriles, hydrocarbons and mixtures thereof.

The alcohols include methanol, ethanol, propanol, isopropanol, butanol,
Ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol,
Can be mentioned. As ethers, propyl ether, isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3
-Dioxolane and 1,3-dioxane. Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone.

Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide. Examples of the esters and lactones include ethyl acetate, methyl acetate, isobutyl acetate, and γ-butyrolactone. Nitriles include acetonitrile, propionitrile, and butyronitrile. Examples of the hydrocarbons include linear or branched hydrocarbons such as pentane, hexane, heptane, and octane, cyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as toluene and xylene. it can.

Preferred solvents are propyl ether and
Isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolan, 1,3-dioxane, acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, ethyl acetate, and γ-butyrolactone are exemplified. be able to. Examples of the mixed solvent system include ethers, ethers and ketones, ethers and esters and lactones, ketones and esters and lactones.

Preferred mixed solvent systems are propyl ether and tetrahydrofuran, and propyl ether and 1,4
-Dioxane, propyl ether and 1,3-dioxolan, isopropyl ether and tetrahydrofuran, isopropyl ether and 1,4-dioxane, isopropyl ether and 1,3-dioxolan, tetrahydrofuran and 1,3-dioxolan, propyl ether and methyl ethyl ketone, propyl ether And methyl isopropyl ketone, isopropyl ether and methyl ethyl ketone, isopropyl ether and methyl isopropyl ketone, tetrahydrofuran and methyl ethyl ketone, tetrahydrofuran and methyl isopropyl ketone, 1,3-dioxolan and methyl ethyl ketone, 1,3-dioxolan and methyl isopropyl ketone, propyl ether and ethyl acetate , Propyl ether and γ-butyrolactone, isopropyl ether and acetic acid Chill, isopropyl ether and γ
-Butyrolactone, tetrahydrofuran and ethyl acetate,
Tetrahydrofuran and γ-butyrolactone, 1,3-dioxolane and ethyl acetate, 1,3-dioxolane and γ-
Butyrolactone, methyl ethyl ketone and ethyl acetate, methyl ethyl ketone and γ-butyrolactone, methyl isopropyl ketone and ethyl acetate, methyl isopropyl ketone and γ-butyrolactone.

The amount of the reaction solvent used varies depending on the target molecular weight, the monomer used, the type of initiator used, and the like. However, considering a solution of the monomer and the solvent, the monomer concentration is 20% by weight or more.
It is preferably at least 30% by weight, more preferably 4% by weight.
The polymerization solvent is used so as to be 0% by weight or more.

The following are examples of the radical initiator that can be used in the polymerization reaction in the present invention. As the radical initiator, those generally used such as a peroxide and an azo initiator can be used. Preferred are azo-based initiators.

As azo initiators, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile),
2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile,
2,2′-azobis (2-methylbutyronitrile),
1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-
Azobis (2-methyl-N-2-propenylpropionamidine) dihydrochloride, 2,2′-azobis [2
-(5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide ｝, Dimethyl 2,
2′-azobis (2-methylpropionate), 4,
4'-azobis (4-cyanovaleric acid),
2,2′-azobis (2- (hydroxymethyl) propionitrile) can be mentioned.

Preferably, 2,2'-azobis (2,4-
Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1
-Carbonitrile), dimethyl 2,2'-azobis (2
-Methylpropionate), 4,4'-azobis (4-
Cyanovaleric acid), 2,2′-azobis (2
-(Hydroxymethyl) propionitrile).

In the present invention, after the polymerization reaction as described above, the obtained polymer (resin) is preferably recovered by a reprecipitation method. That is, after completion of the polymerization, the polymerization reaction liquid is charged into the reprecipitation liquid, and the target resin is recovered as a powder.

Examples of the reprecipitated liquid include water, alcohols, ethers, ketones, amides, esters and lactones, nitriles, hydrocarbons and mixtures thereof.

The alcohols include methanol, ethanol, propanol, isopropanol, butanol,
Examples include ethylene glycol, propylene glycol, and 1-methoxy-2-propanol. As ethers, propyl ether, isopropyl ether,
Butyl methyl ether, tetrahydrofuran, 1,4-
Examples thereof include dioxane, 1,3-dioxolan, and 1,3-dioxane.

As ketones, acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone,
Methyl isobutyl ketone can be mentioned.
As amides, N, N-dimethylformamide, N,
N-dimethylacetamide can be mentioned. Examples of the esters and lactones include ethyl acetate, methyl acetate, isobutyl acetate, and γ-butyrolactone. Nitriles include acetonitrile, propionitrile, and butyronitrile.

The hydrocarbons include pentane, hexane,
Examples thereof include straight-chain or branched hydrocarbons such as heptane and octane, cyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as toluene and xylene. As the mixed liquid system, a mixed liquid system between alcohols, a mixed liquid system between hydrocarbons, a hydrocarbon / alcohol system, a hydrocarbon / ether system, a hydrocarbon / ketone system, a hydrocarbon / ester and Lactones can be mentioned.

Specific examples of a mixed liquid system between alcohols include methanol and ethanol, methanol and propanol, methanol and isopropanol, methanol and butanol, ethylene glycol and ethanol, ethylene glycol and propanol, ethylene glycol and isopropanol, and ethylene glycol. Butanol, 1-methoxy-2-propanol and ethanol, 1-methoxy-2-propanol and propanol, 1-methoxy-2
-Propanol and isopropanol, 1-methoxy-2
-Specific examples of a mixed liquid system between propanol and butanol and hydrocarbons include commercially available mixed solvents such as Isopar G, hexane and heptane, hexane and octane, hexane and cyclohexane, hexane and toluene, hexane and xylene, and cyclohexane. Toluene and the like can be mentioned.

Examples of different types of mixed solvent systems include hexane and propanol, hexane and isopropanol, hexane and butanol, hexane and tetrahydrofuran, hexane and acetone, hexane and methyl ethyl ketone, and hexane and γ-butyrolactone. The mixing ratio of the mixed liquid system is from 20/1 to 1/20.

Preferred reprecipitates include commercially available mixed solvents such as hexane and Isopar G, hexane and heptane, hexane and octane, hexane and cyclohexane, hexane and toluene, cyclohexane and toluene, hexane and propanol, hexane and isopropanol, and hexane. Butanol, hexane and tetrahydrofuran, hexane and acetone, hexane and methyl ethyl ketone, hexane and γ-butyrolactone.

JP-A-9-73173 and 10-2
The reprecipitation liquids described in JP-A-07069 and JP-A-10-274852 are extremely dangerous, for example, reprecipitation in a hydrocarbon solvent typified by hexane or heptane. Therefore, it is not preferable. Further, for example, the operation of repeating re-precipitation as described in Japanese Patent Application Laid-Open No. H10-301285 merely increases the amount of waste liquid unnecessarily, resulting in inefficient operation and deterioration of edge roughness. In the present invention, the number of times of reprecipitation may be one to three times, and is preferably one.

The amount of the reprecipitated solution is appropriately set depending on the amount and type of the solvent used during the polymerization and the type of the reprecipitated solution, but is 3 to 100 times the polymerization solution. Preferably 4 times to 5 times
It is 0 times, and more preferably 5 times to 30 times. If the amount is small, separation from the powder to be recovered becomes difficult, and the working efficiency is deteriorated. If the amount is large, the amount of waste liquid increases, which is not preferable in terms of cost.

The molecular weight of the acid-decomposable resin as described above is weight average (Mw: value in terms of polystyrene by GPC method).
And preferably 3,000 to 100,000, more preferably 4,000 to 70,000, and still more preferably 5,
The range is from 000 to 50,000. The higher the molecular weight, the higher the heat resistance and the like, but on the other hand, the lower the developability and the like. Therefore, the balance is adjusted to an appropriate range.

In the resist composition of the present invention, the amount of the acid-decomposable resin in the whole resist composition is preferably 40 to 99.99% by weight, more preferably 5 to 99.99% by weight based on the total solid content.
0 to 99.97% by weight.

Preferred specific examples of the combination of the repeating structural units of the acid-decomposable resin as the component (A) are shown below.

[0154]

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[0155]

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[0156]

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As the resin of the component (A), the acidic functional group of the alkali-soluble resin (a) having a repeating unit represented by at least one of the following formulas (1a) to (4a) is a substituent. (B) and (b ') protected with
Can be used.

[0158]

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Here, R ⁰¹ is a hydrogen atom or a methyl group, and R ⁰² is a hydroxyl group, a carboxyl group, —R
⁰⁵ COOH, -OR ⁰³ COOH or -OC (= O) R ⁰³
COOH and R ⁰³ is — (CH ₃ ) _n —;
Is an integer of 1 to 4.

[0160]

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Here, the definition of R ⁰¹ is the same as in the above formula (1a).

[0162]

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[0163]

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Here, R ⁰⁴ , R ⁰⁵ , R ⁰⁶ , R ⁰⁷ and R
⁰⁸ is the same or different and is a hydrogen atom or a carbon number 1 to
An alkyl group of 4,

The resin (a) is represented by the formula (1a), the formula (2a),
It may be composed of only the repeating unit represented by the formula (3a) or (4a), or may have another repeating unit. As other repeating units herein, for example, maleic anhydride, fumaronitrile, acrylamide, acrylonitrile, vinylpyridine, vinylpyrrolidone, vinylimidazole, a repeating unit in which the double bond of a monomer containing a double bond such as vinylaniline is cleaved. Can be mentioned.

Formula (1a) in the resin (a) of the present invention,
Although the content of the repeating unit represented by the formula (2a), the formula (3a) and the formula (4a) cannot be determined unconditionally by other contained repeating units, it is usually 15 mol% or more, preferably 20 mol% or more. It is. The molecular weight of the resin (b) of the present invention is preferably a polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “Mw”) measured by gel permeation chromatography (GPC) of 1,000 to 1,000.
150,000, particularly preferably 3,000-100,
000.

The resin (a) can be produced by, for example, polymerizing a corresponding vinyl monomer,
Alternatively, it can be obtained by polycondensing phenols and aldehydes. Among these resins (a), the formula (1a)
Alternatively, the resin containing the repeating unit represented by the formula (2a) can be used as a hydrogenated product having a hydrogenation ratio of 70% or less, preferably 50% or less, and more preferably 40% or less.

The resin (b) is obtained by substituting a hydrogen atom such as a phenolic hydroxyl group or a carboxyl group of the acidic functional group of the resin (a) with a substituted methyl group and a 1-substituted ethyl group (at least one acid selected from the following). An alkali-insoluble or poorly soluble resin substituted with a dissociable group (hereinafter, referred to as "substituent B"), wherein the acid dissociable group is a group capable of dissociating in the presence of an acid. .

Specific examples of the substituent B include methoxymethyl, methylthiomethyl, methoxyethoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiofuranyl, tetrahydrothiopyranyl, and benzyloxymethyl. Phenacyl group, bromophenacyl group, methoxyphenacyl group, α-methylphenacyl group, cyclopropylmethyl group, cyclohexyl group, cyclopentyl group, benzyl group, triphenylmethyl group, diphenylmethyl group, bromobenzyl group, nitrobenzyl group, Substituted methyl groups such as methoxybenzyl group and piperonyl group; 1-substituted ethyl groups such as 1-methoxyethyl group, 1-ethoxyethyl group, isopropyl group, t-butyl group and 1,1-dimethylpropyl group. it can.

Among them, a t-butyl group, a benzyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a tetrahydrothiophenyl group or a tetrahydrothiopyranyl group is preferred.

The introduction of the substituent B is carried out via an acidic functional group of the resin (a), and the substituent B is preferably 15 to 100%, more preferably 15 to 100% of the total acidic functional group of the resin (a). Is introduced in an amount of 30 to 100%. Molecular weight G of resin (b)
Mw measured by PC is preferably 1,000 to 150,
000, particularly preferably 3,000 to 100,000.

In the resin (b ′), a hydrogen atom of a phenolic hydroxyl group or a carboxyl group, which is an acidic functional group of the resin (a), is substituted with an alkoxycarbonyl group (hereinafter, referred to as “substituent B ′”). It is an alkali-insoluble or poorly soluble resin.

Specific examples of the substituent B 'include an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group and a t-butoxycarbonyl group. Among them, a t-butoxycarbonyl group is preferable.

The substituent B 'is introduced through the acidic functional group of the resin (a), and the substituent B' is introduced at 15 to 63% based on the total acidic functional group of the resin (a). The molecular weight of the resin (b ') is preferably from 1,000 to 150,000, more preferably from 3,000 as measured by GPC.
0 to 100,000.

Resins (b) and (b) ′ are alkali-insoluble or hardly soluble. Poor alkali solubility refers to the case where the same alkali development is performed using only the resin (b) and (b) ′ instead of the resist film under suitable alkali development conditions when a pattern is formed on the resist film. The resin (b) and (b) ′ have a film thickness of 50% or more of the initial film thickness and remain after the operation.

[3] The compound (photoacid generator) which generates an acid upon irradiation with actinic rays or radiation, which is the component (B), will be described below. 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
A compound capable of generating an acid by excimer laser light, electron beam, X-ray, molecular beam or 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 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.

Furthermore, 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, a photoacid generator in which an anion has a fluorine atom is an example of an effective photoacid generator. 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 preferably has the following general formula (A1)
-I) to (A1-III).

[0180]

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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, a propyl group, an n-butyl group, which may have a substituent,
1-4 carbon atoms such as a sec-butyl group and a t-butyl group
Individual ones. 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. As the halogen atom for R _{1 to} R ₃₇ , a fluorine atom,
Examples include 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.
As these substituents, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, or an iodine atom), an aryl group having 6 to 10 carbon atoms,
Examples include six alkenyl groups, cyano groups, hydroxy groups, carboxy groups, alkoxycarbonyl groups, nitro groups, and the like.

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 (A1-64) of the photoacid generators represented by the general formulas (A1-I) to (A1-III) are shown below.

[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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Furthermore, 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).

[0192]

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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.

[0194]

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

[0196]

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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 through a single bond or a substituent. Specific examples include the following compounds, but are not limited thereto.

[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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

[0207]

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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.

[0209]

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[0210]

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[0211]

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

[0213]

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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.

[0215]

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The amount of the photoacid generator 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 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 components has a viscosity at 25 ° C. of 6.0 mPa · sec or less, preferably 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, as the component (E), a nitrogen-containing basic compound having no acidic group. This has the effect of improving edge roughness. 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.

[0224]

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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.

[0226]

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

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

[0241]

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.

(1) Synthesis of Resin (1) -1 (Divisional Addition Method, With Initiator Added) The following tetracarboxylic acid obtained by the reaction of acrylic acid ester of 3-oxo-1,1-dimethylbutanol with cyclopentadiene An equimolar mixture of the cyclododecene derivative (1-1) and maleic anhydride was charged into a separable flask and heated at 80 ° C under a nitrogen atmosphere. When the reaction temperature became stable, 1 radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added.
The reaction was started by adding mol%. After heating for 2 hours,
mol-% V-601 was added, and the mixture was further heated for 2 hours. Further, 1 mol% of V-601 was added, and the mixture was further heated for 12 hours.
Thereafter, 1 mol% of V-601 was added, and after heating for 3 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then poured into a mixed solution of hexane / isopropyl alcohol = 2/1 to precipitate a white powder. Was. The precipitated powder was taken out by filtration and dried to obtain the intended resin (1-1). When molecular weight analysis of the obtained resin (1-1) by GPC was attempted, it was 9600 (weight average) in terms of polystyrene. The remaining monomer area ratio is 1.8.
%Met. Further, the resin (1-
It was confirmed that the ratio of the repeating unit of tetracyclododecene and the repeating unit of maleic anhydride in 1) was 1/1.

[0243]

Embedded image

(2) Synthesis of resin (1) -2 (batch addition method, with addition of initiator) The above-mentioned tetra obtained by reaction of acrylic acid ester of 3-oxo-1,1-dimethylbutanol with cyclopentadiene. An equimolar mixture of the cyclododecene derivative (1-1) and maleic anhydride was charged into a separable flask and heated at 80 ° C under a nitrogen stream. When the reaction temperature was stabilized, 3 mol of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added.
The reaction was started by adding 1% and heated for 12 hours. Then 1
After adding mol-% V-601 and heating for 3 hours, the reaction mixture was diluted twice with tetrahydrofuran and then poured into a mixed solution of hexane / isopropyl alcohol = 2/1 to precipitate white powder. The precipitated powder was taken out by filtration, and dried to obtain a target resin (1) -2. The molecular weight analysis of the obtained resin (1) -2 by GPC was 9200 (weight average) in terms of polystyrene. The remaining monomer area ratio was 3.3%. From the NMR spectrum, it was confirmed that the ratio of the tetracyclododecene repeating unit to the maleic anhydride repeating unit of the resin (1) -2 was 1/1.

(3) Synthesis of Resin (1) -3 (drop polymerization,
With the addition of an initiator) An equimolar mixture of the above tetracyclododecene derivative (1-1) and maleic anhydride obtained by the reaction of an acrylate of 3-oxo-1,1-dimethylbutanol with cyclopentadiene is used. It was dissolved in a mixed solvent of tetrahydrofuran / methyl ethyl ketone = 1/1 to prepare a solution having a concentration of 60%. This 1/5 solution was charged into a separable flask, and 1.5 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to the remaining solution. The reaction vessel was heated at 70 ° C. under a nitrogen stream, and when the reaction temperature was stabilized, 0.5 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. Continue with the remaining monomer solution for 8
The mixture was added dropwise over a period of time, and heated for 4 hours after completion of the addition. Then, after adding 1 mol% of V-601 and heating for 3 hours,
Hexane / isopropyl alcohol = 5 /
The mixture was poured into the mixed solution of No. 1 to precipitate a white powder. The precipitated powder is filtered out, dried, and the target resin (1)
-3 was obtained. When the molecular weight analysis of the obtained resin (1) -3 by GPC was attempted, it was 7100 in terms of polystyrene.
(Weight average). The remaining monomer area ratio was 2.3%. From the NMR spectrum, it was confirmed that the ratio of the repeating unit of tetracyclododecene to the repeating unit of maleic anhydride in the resin (1) -3 was 1/1.

The resins ((2) -1 to (12) -2) shown in Table 1 were synthesized by the same operation as in the above synthesis example (the number of the repeating unit is the resin of (2) to (12) described above). Represents the order from the left of the repeating unit in the structure of). Table 1 shows the molar ratio, weight average molecular weight, and residual monomer amount of each repeating unit of the resins (2) -1 to (12) -2.

[0247]

[Table 1]

The polymerization method is as follows. Batch A: Batch addition of initiator, with addition of initiator Batch B: Batch addition of initiator, without addition of initiator Split A: Split addition of initiator, with addition of initiator Split B: Split addition of initiator, addition of initiator No addition Drop A: Drop polymerization, with addition of initiator Drop B: Drop polymerization, without addition of initiator The initiator used is the aforementioned radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd.

Further, the solvents used are as follows. Solvent a: isopropyl alcohol solvent b: isopropyl ether solvent c: tetrahydrofuran solvent d: acetone solvent e: methyl ethyl ketone solvent f: ethyl acetate solvent g: γ-butyrolactone solvent h: hexane solvent i: Isopar G solvent j: toluene

Examples 1 to 18 and Comparative Examples 1 to 8 [Preparation of Radiation-Sensitive Resist Composition] Alkali-soluble resin 1.37 g Photoacid generator 30 mg Basic compound 1.5 mg (D) Compound 3.0 mg If necessary 30 mg of a surfactant was blended 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 2. Further, as Comparative Examples 1 to 8, the radiation-sensitive resin composition was prepared in the same manner as in Examples 1 to 18, except that the above-mentioned resin, photoacid generator, and a basic compound not corresponding to the above-mentioned component (D) were used. Prepared.

[0251]

[Table 2]

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 solvent is 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 exposed to light while changing the exposure amount and focus by mounting a resolution mask on an ArF excimer laser stepper. Then, after heating in a clean room at 125 ° C. for 90 seconds, a tetramethylammonium hydroxide developing solution (2.38% by weight) was used.
It was developed for 0 second 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 the 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 3 shows the results.

[0260]

[Table 3]

As shown in Table 3, the radiation-sensitive resist composition of the present invention showed excellent performance in all evaluation items.

[0262]

According to the present invention, it is possible to provide a radiation-sensitive resist composition having excellent resolving power and preservability and a radiation-sensitive resist composition having further improved edge roughness in the production of semiconductor devices.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 504 504 H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA00 AA02 AA03 AB16 AC01 AC08 AD03 BE00 BG00 CC03 CC04 CC20 FA03 FA12 FA17 4J002 AA031 BH021 BK001 EA017 EA057 EB116 ED027 EE037 EE047 EH007 EH037 EH157 EL067 EN118 EP017 EU018 EU0EU EU138 EU38 EU38 EU38 EU38

Claims (5)

[Claims] 1. A resin whose dissolution rate in an alkali developer changes by the action of an acid, (B) a photoacid generator, (C) a solvent, and (D) a compound represented by the following general formula (1): A radiation-sensitive resist composition comprising an alicyclic or aromatic compound. 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. (A) a resin whose dissolution rate in an alkali developing solution is changed by the action of an acid; (B) a photoacid generator; (C) a solvent; and (D) the following general formula (2): ) Or a radiation-sensitive resist composition comprising the alicyclic compound represented by (4). Embedded image In each formula, R ₁ represents a hydrogen atom or a substituent. Two R ₁ in formulas (3) and (4) may be the same or different. R ₂ represents a substituent. n shows 0-6. 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. 3. The viscosity at 25 ° C. is 6.0 mPa.s. sec
The radiation-sensitive resist composition according to claim 1, wherein: 4. The radiation-sensitive resist composition according to claim 1, further comprising (E) a nitrogen-containing basic compound having no acidic group. 5. The method according to claim 1, further comprising (F) a fluorine-based and / or silicon-based surfactant.
The radiation-sensitive resist composition according to any one of the above.