JP2003202673A - Radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition excellent in basic physical properties as a resist, such as transparency and sensitivity to radiations, resolution and dry etching resistance. <P>SOLUTION: The radiation-sensitive resin composition comprises an acid- dissociable group-containing resin (A) including a repeating unit of formula (1-1) (where each R<SP>1</SP>is independently H or methyl and each R<SP>2</SP>is independently a 2-6C alkyl) and a radiation-sensitive acid generator (B) of formula (2) (where R<SP>3</SP>is a monovalent organic group and R<SP>4</SP>is a divalent organic group). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a radiation-sensitive resin composition, and more specifically, charged particles such as deep ultraviolet rays represented by KrF excimer laser or ArF excimer laser, X-rays such as synchrotron radiation, and electron beams. The present invention relates to a radiation-sensitive resin composition that can be suitably used as a chemically amplified resist useful for fine processing using various kinds of radiation such as rays.

[0002]

2. Description of the Related Art Recently, in the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration,
There is a need for a lithography technique capable of fine processing at a level of 0.20 μm or less. In the conventional lithography process, near-ultraviolet rays such as i-rays are generally used as radiation, but it is said that the near-ultraviolet rays are extremely difficult to perform fine processing on the subquarter micron level. Therefore, in order to enable fine processing at a level of 0.20 μm or less, use of radiation having a shorter wavelength is being studied. Examples of such short-wave radiation include bright line spectra of mercury lamps, deep ultraviolet rays represented by excimer lasers, X-rays, electron beams, and the like. Of these, the KrF excimer laser (wavelength 248 nm) or the ArF excimer laser (wavelength 193 nm) is receiving attention.

As a resist suitable for irradiation by such an excimer laser, a component having an acid dissociable group and a component which generates an acid upon irradiation with radiation (hereinafter referred to as "exposure") (hereinafter referred to as "acid generator"). A lot of resists (hereinafter, referred to as "chemically amplified resists") that utilize the chemical amplification effect of () are proposed. For example, in Japanese Patent Publication No. 27660/1990, a polymer in which a carboxylic acid is protected by a t-butoxycarbonyl group or a polymer in which a phenolic hydroxyl group is protected by a t-butoxycarbonyl group,
A resist containing an acid generator has been proposed. In the resist, the t-butoxycarbonyl group in the polymer is dissociated by the action of the acid generated by the exposure to have an acidic group consisting of a carboxyl group or a phenolic hydroxyl group, and the exposed area of the resist film is alkaline. It utilizes the phenomenon that it becomes easily soluble in a developing solution. Most of the conventional chemically amplified resists are based on phenolic resins.

However, in the case of a chemically amplified resist based on a phenolic resin, when far ultraviolet rays are used as radiation, the far ultraviolet rays are absorbed due to the aromatic ring in the resin, and thus the exposed far ultraviolet rays are exposed. However, there is a drawback that the lower layer of the resist coating cannot be sufficiently reached. Therefore, the exposure amount is large in the upper layer portion of the resist film and small in the lower layer portion, and as a result, the upper portion of the resist pattern after development becomes a trapezoidal shape that becomes thinner toward the lower portion and sufficient resolution cannot be obtained. The problem arises. If the resist pattern after development becomes trapezoidal in this way, the next step,
That is, when etching or implanting ions, desired dimensional accuracy cannot be achieved, which is a problem. Further, if the shape of the upper portion of the resist pattern is not rectangular, the rate of disappearance of the resist due to dry etching becomes high, and there is a problem that it becomes difficult to control etching conditions.

On the other hand, the shape of the resist pattern can be improved by increasing the radiation transmittance of the resist film. For example, a (meth) acrylate resin represented by polymethylmethacrylate is a highly preferable resin from the viewpoint of radiation transmittance since it has high transparency even to deep ultraviolet rays, and is disclosed in JP-A-4-226461. , A chemically amplified resist using a methacrylate resin has been proposed. However, although this composition is excellent in terms of microfabrication performance, it does not have an aromatic ring and therefore has a drawback of low dry etching resistance. Therefore, also in this case, it is difficult to perform highly accurate etching processing, and it cannot be said that it has both transparency to radiation and dry etching resistance.

Further, as one of the methods for improving the dry etching resistance without impairing the transparency of the chemically amplified resist to radiation, an aliphatic ring is introduced into the resin component in the resist instead of the aromatic ring. The method is known. For example, JP-A-7-234511 proposes a chemically amplified resist using a (meth) acrylate resin having an aliphatic ring.

However, in the chemically amplified resist,
It is known that the acid-labile group has a great influence on the function of the resist. That is, it is known that the dissociation reaction rate of the protective group dissociated by the acid generated by exposure has a great influence on the resist performance, such as sensitivity, resolution, exposure margin, and focus tolerance. For example, with a resin component having a group that is relatively easily dissociated by an acid (for example, an acetal-based functional group such as a tetrahydropyranyl group), the basic physical properties of the chemically amplified resist, particularly the sensitivity and the pattern shape, are good, There is a problem in storage stability as a composition. On the other hand, a resin component having a group that is relatively difficult to dissociate with an acid (for example, a t-butyl functional group such as a t-butyl group and a t-butoxycarbonyl group) has good storage stability on the contrary, There is a drawback in that the basic physical properties of the chemically amplified resist, particularly the sensitivity and pattern shape, are impaired. Further, when an aliphatic ring is introduced into the resin component in the chemically amplified resist, the hydrophobicity of the resin itself becomes very high, and there is a problem in terms of adhesiveness to the substrate.

Further, when forming a resist pattern using a chemically amplified resist, heat treatment is usually carried out after exposure to accelerate the dissociation of acid dissociable groups, but normally when the heating temperature changes. It is inevitable that the line width of the resist pattern also varies to some extent. However, reflecting the miniaturization of integrated circuit elements in recent years, there has been a strong demand for development of a resist having a small heating temperature dependency (that is, a process margin) after exposure.

Further, in the chemically amplified resist, it is known that the acid generator has a great influence on the function as the resist. Today, onium salt compounds are widely used as acid generators for chemically amplified resists because of their high quantum yield of acid generation by exposure and high sensitivity. As the onium salt compound, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate and the like are used. However, these conventional onium salt compounds are generally unsatisfactory in terms of sensitivity, and even when the sensitivity is relatively high, when the transparency of the resulting resist film is insufficient or the diffusion rate of the acid generated is Since adjustment may be difficult in some cases, it cannot be said that the resist performance that integrates the resolution, the pattern shape, and the like is sufficient.

Under such circumstances, from the viewpoint of technological development capable of coping with the progress of miniaturization in integrated circuit elements, it can be applied to short wavelength radiation represented by far ultraviolet rays and has high transparency to radiation. In addition, there has been a strong demand for a chemically amplified resist having excellent basic physical properties as a resist such as sensitivity, resolution and pattern shape.

[0011]

The present invention has been made in view of the above circumstances and has high transparency to radiation and excellent basic physical properties as a resist such as sensitivity, resolution, dry etching resistance, and pattern shape. An object of the present invention is to provide a radiation sensitive resin composition useful as a chemically amplified resist having a wide process margin.

[0012]

The radiation-sensitive resin composition of the present invention has the following general formulas (1-1) to (1) as repeating units.
An acid-labile group-containing resin (A) containing at least one of the repeating units represented by (1-5) (hereinafter, referred to as “resin (A)”) and represented by the following general formula (2). And a radiation-sensitive acid generator (B). Further, the above general formulas (1-1) to (1-5) of the present invention
The total content of repeating units represented by can be 5 to 50 mol% in 100 mol% of all repeating units of the resin (A). Furthermore, the following general formula (1-1)
In (1-4), R ² can be an ethyl group.

[0013]

[Chemical 3]

[Chemical 4] [In the general formula (1-1) ~ (1-5), R 1 represents a hydrogen atom or a methyl group independently of one another, ^{R 2} is an alkyl group having 2 to 6 carbon atoms independently of one another. In addition, in the general formula (2), R ³ represents a monovalent organic group, and R ⁴ represents a divalent organic group. ]

[0014]

INDUSTRIAL APPLICABILITY The radiation-sensitive resin composition of the present invention contains an actinic ray such as a KrF excimer laser (wavelength 248 nm) by combining a specific resin and an acid generator.
Alternatively, as a chemically amplified resist sensitive to deep ultraviolet rays represented by ArF excimer laser (wavelength 193 nm), a resist having high transparency, high resolution, and sensitivity, dry etching resistance, pattern shape, etc. It has excellent basic physical properties. In addition, the radiation-sensitive resin composition of the present invention has good adhesiveness to the substrate and good hem shape of the pattern. The radiation-sensitive resin composition of the present invention can be extremely suitably used for manufacturing integrated circuit devices, which are expected to be further miniaturized in the future.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. <1> Resin (A) The resin (A) of the present invention is a resin having at least one of the repeating units represented by the general formulas (1-1) to (1-5). The resin (A) of the present invention is insoluble or sparingly soluble in alkali before the ester bonds contained in the repeating units represented by the general formulas (1-1) to (1-5) are dissociated. However, when the ester bond is dissociated by the action of an acid to form a carboxyl group, it becomes alkali-soluble. Here, the above-mentioned "alkali-insoluble or alkali-insoluble" means that under alkaline development conditions adopted when forming a resist pattern from a resist coating formed from a radiation-sensitive resin composition containing this resin, This means the property that when a film using only a resin instead of the resist film is developed, 50% or more of the initial film thickness of the film remains after development.

The resin (A) of the present invention may contain at least one kind of repeating units represented by the general formulas (1-1) to (1-5) as a repeating unit. That is, the resin (A) of the present invention may contain only one kind of the repeating units represented by the general formulas (1-1) to (1-5), and the general formula (1
2 of the repeating units represented by -1) to (1-5)
It may contain more than one species. A resist film having high transparency can be obtained by the resin (A) having such a constitution, and by combining with the acid generator represented by the general formula (2), a resist excellent in sensitivity, resolution and the like can be obtained. Is obtained. The resin (A) is 1
They may be used alone or in combination of two or more.

In the above general formulas (1-1) to (1-5), R
^1's each independently represent a hydrogen atom or a methyl group. Also,
R ² represents an alkyl group having 2 to 6 carbon atoms independently of one another.
Specific examples thereof include an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group and the like, and among these, an ethyl group is particularly preferable.
As the resin (A), the general formulas (1-1) to (1-
When two or more of the repeating units represented by 5) are included, each R ¹ and each R ² may be the same atom or group or different atoms or groups. In addition, the above resin (A)
In the case where two or more of the repeating units represented by the general formulas (1-1) to (1-5) are contained as repeating units, each R ¹ and each R ² are the same atom. Alternatively, it may be a group or different atoms or groups.

Examples of the monomer giving the repeating units represented by the above general formulas (1-1) to (1-5) are represented by the following general formulas (5-1) to (5-5). Compounds and the like. In addition, the following general formulas (5-1) to (5-5)
Where R ¹ and R ² are each represented by the general formula (1-1) to
It is the same as the definition of R ¹ and R ^{2 in} (1-5).

[0019]

[Chemical 5]

Further, the above resin (A) has the above general formula (1)
The structure is not particularly limited as long as it contains at least one of the repeating units represented by -1) to (1-5). For example, the resin (A) is a repeating unit other than the repeating units represented by the general formulas (1-1) to (1-5) (hereinafter, referred to as “other repeating unit”).
You may have 1 or more types. Examples of the polymerizable unsaturated monomer that gives such another repeating unit include monofunctional monomers and polyfunctional monomers exemplified below. Monofunctional monomer [1] norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclodecanyl (meth) acrylate,
(Meth) acrylic acid dicyclopentenyl, (meth) acrylic acid adamantyl, (meth) acrylic acid 3-hydroxy-adamantan-1-yl ester, (meth) acrylic acid adamantyl methyl, (meth) acrylic acid 6-
(3,3,3-Trifluoro-2-hydroxy-2-trifluoromethyl-propyl) -bicyclo [2.2.
1] (meth) acrylic acid esters having a bridged hydrocarbon skeleton such as hept-2-yl ester; [2] (meth) acrylic acid carboxynorbornyl,
Carboxytricyclodecanyl (meth) acrylate,
Carboxyl group-containing esters having a bridged hydrocarbon skeleton of unsaturated carboxylic acid such as carboxytetracyclodecanyl (meth) acrylate; [3] Methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) N-propyl acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate, 1-methylpropyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic acid 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,
Cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate,
It also has a bridged hydrocarbon skeleton such as 2-cyclopentyloxycarbonylethyl (meth) acrylate, 2-cyclohexyloxycarbonylethyl (meth) acrylate, and 2- (4-methoxycyclohexyl) oxycarbonylethyl (meth) acrylate. (4) methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, n-propyl α-hydroxymethyl acrylate, n-butyl α-hydroxymethyl acrylate, etc. α-Hydroxymethyl acrylic acid esters; [5] (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, malein nitrile, fumaronitrile, mesacon nitrile, citracon nitrile,
Unsaturated nitrile compounds such as itacone nitrile; [6] Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citracone amide, itaconamide; 7] Other nitrogen-containing vinyl compounds such as N- (meth) acryloylmorpholine, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine and vinylimidazole; [8] (meth) acrylic acid, crotonic acid, maleic acid acid,
Unsaturated carboxylic acids (anhydrides) such as maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;

[9] 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, (meth) acrylic acid 4
-Carboxyl group-containing esters of unsaturated carboxylic acids such as carboxybutyl and 4-carboxycyclohexyl (meth) acrylate that do not have a bridged hydrocarbon skeleton; [10] A compound represented by the following chemical formula (3) 1, α-
(Meth) acryloyloxy-β-methoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-ethoxycarbonyl-γ-butyrolactone, α
-(Meth) acryloyloxy-β-n-propoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-i-propoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-n
-Butoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β- (2-methylpropoxy) carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β- (1-methylpropoxy) carbonyl-γ- Butyrolactone, α- (meth) acryloyloxy-β-t-butoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-cyclohexyloxycarbonyl-γ-butyrolactone, α-
(Meth) acryloyloxy-β- (4-t-butylcyclohexyloxy) carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-phenoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β- (1-Ethoxyethoxy) carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β- (1-cyclohexyloxyethoxy) carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-t-butoxycarbonylmethoxy Carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-tetrahydrofuranyloxycarbonyl-
γ-butyrolactone, α- (meth) acryloyloxy-β-tetrahydropyranyloxycarbonyl-γ-butyrolactone, α-methoxycarbonyl-β- (meth)
Acryloyloxy-γ-butyrolactone, α-ethoxycarbonyl-β- (meth) acryloyloxy-γ-
Butyrolactone, α-n-propoxycarbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-I-propoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-n-butoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α- (2-methylpropoxy) carbonyl-
β- (meth) acryloyloxy-γ-butyrolactone, α- (1-methylpropoxy) carbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-T-butoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-cyclohexyloxycarbonyl-β- (meth) acryloyloxy-γ-
Butyrolactone, α- (4-t-butylcyclohexyloxy) carbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-phenoxycarbonyl-β
-(Meth) acryloyloxy-γ-butyrolactone,
α- (1-ethoxyethoxy) carbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-
(1-Cyclohexyloxyethoxy) carbonyl-β
-(Meth) acryloyloxy-γ-butyrolactone,
α-t-butoxycarbonylmethoxycarbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
(Tetrahydrofuranyloxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-tetrahydropyranyloxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone and other (meth) acryloyloxy having an acid-labile group Lactone compound; [11] α- (meth) acryloyloxy-β-fluoro-γ-butyrolactone, α- (meth) acryloyloxy-β-hydroxy-γ-butyrolactone, α- (meth) acryloyloxy-β-methyl- γ-butyrolactone, α- (meth) acryloyloxy-β-ethyl-
γ-butyrolactone, α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone, α- (meth) acryloyloxy-β-methoxy-γ-butyrolactone, α-fluoro-β- (meth) acryloyloxy- γ-butyrolactone, α-hydroxy-β- (meth) acryloyloxy-γ-butyrolactone, α-methyl-β- (meth) acryloyloxy-γ-butyrolactone, α-ethyl-β- (meth) acryloyloxy-γ- Acids such as butyrolactone, α, α-dimethyl-β- (meth) acryloyloxy-γ-butyrolactone, α-methoxy-β- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-δ-mevalonolactone (Meth) acryloyloxylactone compound having no dissociative group;

[0021]

[Chemical 6]

Polyfunctional monomer [1] 1,2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth) acrylate, tricyclo Polyfunctional monomer having a bridged hydrocarbon skeleton such as decanyl dimethylol di (meth) acrylate; [2] Methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth ) Acrylate, 1,6-hexanediol di (meth) acrylate, 2,5-dimethyl-
2,5-hexanediol di (meth) acrylate,
1,8-octanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, 1,
A polyfunctional monomer having no bridged hydrocarbon skeleton such as 4-bis (2-hydroxypropyl) benzenedi (meth) acrylate and 1,3-bis (2-hydroxypropyl) benzenedi (meth) acrylate;

Among the polymerizable unsaturated monomers which give these other repeating units, dicyclopentenyl (meth) acrylate, adamantyl acrylate (meth), and 3-hydroxy-adamantane-1-methacrylate (meth) acrylate. Yl ester, (meth) acrylic acid 6- (3,3,3-trifluoro-2-hydroxy-2-trifluoromethyl-propyl) -bicyclo [2.2.1] hept-2-yl ester, etc. (Meth) acrylic acid esters having a bridged hydrocarbon skeleton, α- (meth) acryloyloxy-β-
(Meth) acryloyloxy lactone compounds such as methyl-γ-butyrolactone α- (meth) acryloyloxy-β-methoxy-γ-butyrolactone and α- (meth) acryloyloxy-δ-mevalonolactone have dry etching resistance and developability. From the point, it is particularly preferable.

The above general formula (1-1) in the above resin (A)
The ratio of the repeating units represented by (1-5) to (1-5) can be set in various ranges as required. The general formula (1-
The total content of the repeating units represented by 1) to (1-5) is preferably 5 to 100 mol% of all repeating units.
It is 50 mol%, more preferably 10 to 50 mol%.
Moreover, when using 2 or more types of repeating units represented by said General formula (1-1)-(1-5), the content rate of 1 type of repeating unit is 1-49 mol% normally, Preferably it is 5-. 45
Mol%, more preferably 10 to 40 mol%. By setting the total content of the repeating units represented by the general formulas (1-1) to (1-5) to 5 mol% or more, the contrast during development of the resist can be improved,
It is preferable because a resist having high resolution and no development defect can be obtained. Further, when the content is 50 mol% or less, the contrast to the developing solution can be improved, and a resist having high developability and sensitivity can be obtained, which is preferable.

When the resin (A) contains the other repeating unit, the content of the other repeating unit can be various values as required. The content of the above-mentioned other repeating unit is usually 95 mol% or less, preferably 9 mol% in 100 mol% of all repeating units.
It is 0 mol% or less, more preferably 85 mol% or less, and further preferably 80 mol% or less.

There are no particular restrictions on the molecular weight of the resin (A), and various molecular weights can be used if necessary. Usually, the polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) of the resin (A) by gel permeation chromatography (GPC) is 3000 to 30.
000, preferably 5000-30000, more preferably 5000-25000, more preferably 5000.
~ 20,000. Mw of the above resin (A) is 3000
By setting the above, it is possible to improve the heat resistance when used as a resist, and on the other hand, when it is 30,000 or less, it is possible to suppress a decrease in developability when used as a resist, which is preferable.

The ratio (Mw / Mn) between the Mw of the resin (A) and the polystyrene reduced number average molecular weight by GPC (hereinafter referred to as "Mn") may be set to various values as necessary. You can Usually, the above ratio is 1 to
5, preferably 1-4, more preferably 1-3.
When the content is in this range, the dissolution rate of the resin can be made uniform, which is preferable.

The method for producing the resin (A) is not particularly limited, but usually, a radical polymerization initiator is used together with hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, transition metal catalysts and the like. However, if necessary, it can be obtained by polymerizing the polymerizable unsaturated monomer corresponding to each repeating unit in the presence of a chain transfer agent in a suitable solvent. As the reaction conditions in the above-mentioned polymerization, for example, the reaction temperature can be usually 40 to 120 ° C, preferably 50 to 90 ° C, and the reaction time is
It can be usually 1 to 48 hours, preferably 1 to 24 hours.

Examples of the solvent used in the above polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; cyclohexane, cycloheptane, Cycloalkanes such as cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; halogenated carbonization such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide and chlorobenzene Hydrogens;
Examples thereof include saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; and ethers such as tetrahydrofuran, dimethoxyethanes and diethoxyethanes. The above-exemplified solvents may be used alone or in combination of two or more.

Further, the resin (A) has a sensitivity when used as a resist as the amount of impurities such as halogen and metal decreases.
It is preferable because resolution, process stability, pattern shape and the like can be further improved. Therefore, it is preferable to carry out purification for removing impurities after the production of the resin (A). Examples of the purification method of the resin (A) include chemical purification methods such as reprecipitation, washing with water, and liquid extraction, and physical purification methods such as chemical purification methods such as ultrafiltration and centrifugation. A combination and the like can be mentioned.

<2> Radiation-sensitive acid generator (B) The radiation-sensitive acid generator (B) of the present invention is a compound represented by the above general formula (2). The radiation-sensitive acid generator (B) of the present invention generates an acid by exposure. And
By the action of the acid, the acid dissociable group in the resin (A) is dissociated to make the exposed portion of the resist film readily soluble in an alkali developing solution, so that a positive resist pattern can be formed. The radiation-sensitive acid generator (B) is
They may be used alone or in combination of two or more.

In the above general formula (2), R ³ represents a monovalent organic group, specifically, an alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, and 3 carbon atoms. ~ 1
Examples thereof include a perfluorocycloalkyl group having 0, a bicyclo ring-containing hydrocarbon group having 7 to 15 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Specifically, a methyl group, an ethyl group,
n-propyl group, n-butyl group, n-pentyl group, n-
Alkyl group such as hexyl group, n-octyl group, n-nonyl group, n-decyl group; perfluoro such as trifluoromethyl group, pentafluoroethyl group, nonafluoro-n-butyl group, perfluoro-n-octyl group Alkyl group;
Perfluorocycloalkyl group such as pentafluorocyclohexyl group; Bicyclo ring-containing hydrocarbon group such as group having norbornane skeleton which may be substituted with alkyl group, alkoxyl group, alkoxycarbonyl group, alkylalkoxycarbonyl group, etc .; phenyl group And aryl groups such as perfluorophenyl group, methylphenyl group, trifluoromethylphenyl group, tolyl group, and naphthyl group.

Further, in the general formula (2), R ⁴ represents a divalent organic group, specifically, a methylene group and a carbon number of 2 to 2.
An alkylene group of 0, an aralkylene group having 2 to 20 carbon atoms,
Substitute a difluoromethylene group, a perfluoroalkylene group having 2 to 20 carbon atoms, a cyclohexylene group, a group having an optionally substituted norbornane skeleton, a phenylene group, and an aryl group or an alkoxyl group having 2 or more carbon atoms for these groups. Examples include groups introduced as groups.

The above radiation-sensitive acid generator (B) includes
Specifically, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N
-(Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] ] Hept-5
Ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethylsulfonyl) Oxy) naphthylimide, N- (trifluoromethylsulfonyloxy) -1,2-cyclohexanedicarboximide, N
-(Trifluoromethylsulfonyloxy) tetrafluorosuccinimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-2,3
-Dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.2] octane-2,
3-dicarboximide, N- (trifluoromethylsulfonyloxy) cyclobutanedicarboximide, N
-(Trifluoromethylsulfonyloxy) cyclopentanedicarboximide, N- (trifluoromethylsulfonyloxy) -1,2-cyclohexanedicarboximide, N- (trifluoromethylsulfonyloxy) tetrafluorosuccinimide, N- (tri Fluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.2]
Octane-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) cyclobutanedicarboximide, N- (trifluoromethylsulfonyloxy) cyclopentanedicarboximide, N- (10-
Camphorsulfonyloxy) succinimide, N-
(10-camphorsulfonyloxy) phthalimide,
N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1
0-camphorsulfonyloxy) bicyclo [2.2.
1] Heptane-5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) -1,2-cyclohexanedicarboximide, N
-(10-camphorsulfonyloxy) tetrafluorosuccinimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [ 2.2.2] Octane-2,3-dicarboximide, N- (10-camphorsulfonyloxy) cyclobutanedicarboximide, N- (10
-Camphorsulfonyloxy) cyclopentanedicarboximide, N- (n-octanesulfonyloxy)
Succinimide, N- (n-octanesulfonyloxy) phthalimide, N- (n-octanesulfonyloxy) diphenylmaleimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (n-octanesulfonyloxy) -7-oxabicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N-
(N-Octanesulfonyloxy) bicyclo [2.2.
1] Heptane-5,6-oxy-2,3-dicarboximide, N- (n-octanesulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy)-
1,2-cyclohexanedicarboximide, N- (n
-Octanesulfonyloxy) tetrafluorosuccinimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] heptane-2,3-dicarboximide, N- (n-octanesulfonyloxy) bicyclo [2.2] .2] Octane-2,3-dicarboximide, N- (n-octanesulfonyloxy) cyclobutanedicarboximide, N- (n-octanesulfonyloxy) cyclopentanedicarboximide, N- (p
-Toluenesulfonyloxy) succinimide, N-
(P-toluenesulfonyloxy) phthalimide, N-
(P-Toluenesulfonyloxy) diphenylmaleimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) -7
-Oxabicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] heptane-5
6-oxy-2,3-dicarboximide, N- (p-
Toluenesulfonyloxy) naphthylimide, N- (p
-Toluenesulfonyloxy) -1,2-cyclohexanedicarboximide, N- (p-toluenesulfonyloxy) tetrafluorosuccinimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] heptane-2,3 -Dicarboximide, N- (p-toluenesulfonyloxy) bicyclo [2.2.2] octane-2,3-dicarboximide, N- (p-toluenesulfonyloxy) cyclobutanedicarboximide, N
-(P-toluenesulfonyloxy) cyclopentanedicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethyl) Benzenesulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-Trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (2-trifluoromethylbenzenesulfonyloxy) -1,2
-Cyclohexanedicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) tetrafluorosuccinimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-2,3-dicarboxy Imido, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.2] octane-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) cyclobutanedicarboximide, N -(2-
Trifluoromethylbenzenesulfonyloxy) cyclopentanedicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N
-(4-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N-
(4-trifluoromethylbenzenesulfonyloxy)
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3- Dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4-trifluoromethylbenzenesulfonyloxy) -1,2-cyclohexanedicarboximide, N- (4-trifluoromethylbenzene Sulfonyloxy) tetrafluorosuccinimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.2] Octane-2,3-dicarboximide, N (4-Trifluoromethylbenzenesulfonyloxy) cyclobutanedicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) cyclopentanedicarboximide, N- (perfluorobenzenesulfonyloxy) succinimide, N- (perfluorobenzene Sulfonyloxy) phthalimide, N- (perfluorobenzenesulfonyloxy) diphenylmaleimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorobenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] Heptane 5,6-oxy-2,3-dicarboximide, N- (perfluoro benzenesulfonyloxy) naphthylimide, N-
(Perfluorobenzenesulfonyloxy) -1,2-
Cyclohexanedicarboximide, N- (perfluorobenzenesulfonyloxy) tetrafluorosuccinimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] heptane-2,3-dicarboximide, N- (perfluoro Benzenesulfonyloxy) bicyclo [2.2.2] octane-2,3-dicarboximide, N- (perfluorobenzenesulfonyloxy) cyclobutanedicarboximide, N-
(Perfluorobenzenesulfonyloxy) cyclopentanedicarboximide, N- (naphthalenesulfonyloxy) succinimide, N- (naphthalenesulfonyloxy) phthalimide, N- (naphthalenesulfonyloxy) diphenylmaleimide, N- (naphthalenesulfonyloxy) bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (naphthalenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N-
(Naphthalenesulfonyloxy) bicyclo [2.2.
1] Heptane-5,6-oxy-2,3-dicarboximide, N- (naphthalenesulfonyloxy) naphthylimide, N- (naphthalenesulfonyloxy) -1,2
-Cyclohexanedicarboximide, N- (naphthalenesulfonyloxy) tetrafluorosuccinimide,
N- (naphthalenesulfonyloxy) bicyclo [2.
2.1] Heptane-2,3-dicarboximide, N-
(Naphthalenesulfonyloxy) bicyclo [2.2.
2] Octane-2,3-dicarboximide, N- (naphthalenesulfonyloxy) cyclobutanedicarboximide, N- (naphthalenesulfonyloxy) cyclopentanedicarboximide, N-[(5-methyl-5-
Methoxycarbonylbicyclo [2.2.1] heptane-
2-yl) sulfonyloxy] succinimide, N-
[(5-Methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] phthalimide, N-[(5-methyl-5-methoxycarbonylbicyclo [2.2.1] heptane -2-yl) sulfonyloxy] diphenylmaleimide, N-
[(5-Methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N-[(5-methyl-5-methoxycarbonylbicyclo [2.2.1] heptane-2-
Yl) sulfonyloxy] -7-oxabicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N-[(5-methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] bicyclo [2 1.2.1] heptane-5,6-oxy-2,3-dicarboximide, N-[(5-methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] Naphthyl imide,
N-[(5-methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] -1,2-cyclohexanedicarboximide, N
-[(5-Methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] tetrafluorosuccinimide, N-[(5-methyl-5-methoxycarbonylbicyclo [2.2. 1] heptan-2-yl) sulfonyloxy] bicyclo [2.
2.1] Heptane-2,3-dicarboximide, N-
[(5-Methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] bicyclo [2.2.2] octane-2,3-dicarboximide, N-[(5 -Methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] cyclobutanedicarboximide, N
-[(5-Methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] cyclopentanedicarboximide, 2,5-dimethyl-tetrahydro-cyclopentane [1,2-C ;
3,4-C ′] dipyrrole-1,3,4,6-tetraone, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) phthalimide, N- (nonafluoro- n-butanesulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) -7-oxabicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,
3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) -1,2-cyclohexanedicarboximide, N- (nonafluoro-
n-butanesulfonyloxy) tetrafluorosuccinimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] heptane-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) Bicyclo [2.2.2] octane-2,
3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) cyclobutanedicarboximide, N- (nonafluoro-n-butanesulfonyloxy) cyclopentanedicarboximide, N- (perfluoro-n-octanesulfonyloxy) ) Succinimide, N- (perfluoro-n-octanesulfonyloxy) phthalimide, N- (perfluoro-n-octanesulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- (perfluoro-n-octa Sulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) naphthylimide, N- (perfluoro-n- Octanesulfonyloxy) -1,2-cyclohexanedicarboximide, N- (perfluoro-n
-Octanesulfonyloxy) tetrafluorosuccinimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] heptane-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) ) Bicyclo [2.2.2] octane-
2,3-dicarboximide, N- (perfluoro-n
-Octanesulfonyloxy) cyclobutanedicarboximide, N- (perfluoro-n-octanesulfonyloxy) cyclopentanedicarboximide, N-
(Benzenesulfonyloxy) succinimide, N-
(Benzenesulfonyloxy) phthalimide, N- (Benzenesulfonyloxy) diphenylmaleimide, N-
(Benzenesulfonyloxy) bicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N-
(Benzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) bicyclo [2.2.1] heptane-5. 6-oxy-2,3-dicarboximide, N- (benzenesulfonyloxy)
Naphthylimide, N- (benzenesulfonyloxy)-
1,2-cyclohexanedicarboximide, N- (benzenesulfonyloxy) tetrafluorosuccinimide, N- (benzenesulfonyloxy) bicyclo [2.
2.1] Heptane-2,3-dicarboximide, N-
(Benzenesulfonyloxy) bicyclo [2.2.2]
Octane-2,3-dicarboximide, N- (benzenesulfonyloxy) cyclobutanedicarboximide, N- (benzenesulfonyloxy) cyclopentanedicarboximide and the like can be mentioned.

Among these radiation-sensitive acid generators (B), N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N-[(5-methyl-5
-Methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide, N-
[(5-Methyl-5-methoxycarbonylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) -1,2-cyclohexanedicarboximide, N- (perfluoro-n-octanesulfonyloxy) tetrafluorosuccinimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] heptane-2,3
-Dicarboximide, N- (trifluoromethylsulfonyloxy) -1,2-cyclohexanedicarboximide, N- (trifluoromethylsulfonyloxy)
Tetrafluorosuccinimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-2,3-dicarboximide and the like are preferable from the viewpoint of sensitivity and contrast of the resulting resist.

In the present invention, another radiation-sensitive acid generator (hereinafter referred to as "radiation-sensitive acid generator (b)") is used in combination with the radiation-sensitive acid generator (B). You can Examples of the radiation-sensitive acid generator (b) include [1] onium salt compounds such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and pyridinium salts, [2] haloalkyl group-containing hydrocarbon compounds and haloalkyl groups. A halogen-containing compound such as a heterocyclic compound-containing compound, [3] 1,3-diketo-2-diazo compound,
Diazoketone compounds such as diazobenzoquinone compounds and diazonaphthoquinone compounds, [4] β-ketosulfones, β
-Sulfone compounds such as sulfonyl sulfone and α-diazo compounds of these compounds, [5] alkyl sulfonic acid ester, alkyl sulfonic acid imide, haloalkyl sulfonic acid ester, aryl sulfonic acid ester and imino sulfonate, and other sulfonic acid compounds, disulfonyl Diazomethane compound, disulfonylmethane compound,
Examples thereof include oxime sulfonate compounds and hydrazine sulfonate compounds. The above radiation-sensitive acid generator (b) may also be used alone, or 2
You may use together 1 or more types.

Specific examples of the above-mentioned onium salt compound, halogen-containing compound, sulfone compound, sulfonate compound, disulphonyldiazomethane compound, disulphonylmethane compound, oxime sulfonate compound and hydrazine sulfonate compound include the following compounds: Can be mentioned. [1] Onium salt compound triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-
Naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 1-naphthyldimethylsulfonium perfluoro-n-octanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium nonafluoro-
n-butane sulfonate, 1-naphthyl diethyl sulfonium perfluoro-n-octane sulfonate, 1-
(4-hydroxynaphthyl) dimethylsulfonium trifluoromethanesulfonate, 1- (4-hydroxynaphthyl) dimethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-hydroxynaphthyl) dimethylsulfonium perfluoro-n-octanesulfonate, 1- (4-hydroxynaphthyl) diethylsulfonium trifluoromethanesulfonate, 1- (4-hydroxynaphthyl) diethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-hydroxynaphthyl) diethylsulfonium perfluoro-n-octanesulfonate, 1- (4-methylnaphthyl) dimethylsulfonium trifluoromethanesulfonate, 1-
(4-Methylnaphthyl) dimethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-methylnaphthyl) dimethylsulfonium perfluoro-n-octanesulfonate, 1- (4-methylnaphthyl) diethylsulfonium trifluoromethanesulfonate, 1-
(4-methylnaphthyl) diethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-methylnaphthyl) diethylsulfonium perfluoro-n-octanesulfonate, 1- (4-cyanonaphthyl) dimethylsulfonium trifluoromethanesulfonate, 1-
(4-Cyanonaphthyl) dimethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-cyanonaphthyl) dimethylsulfonium perfluoro-n-octanesulfonate, 1- (4-cyanonaphthyl) diethylsulfonium trifluoromethanesulfonate, 1-
(4-Cyanonaphthyl) diethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-cyanonaphthyl) diethylsulfonium perfluoro-n-octanesulfonate, 1- (4-nitronaphthyl) dimethylsulfonium trifluoromethanesulfonate, 1-
(4-Nitronaphthyl) dimethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-nitronaphthyl) dimethylsulfonium perfluoro-n-octanesulfonate, 1- (4-nitronaphthyl) diethylsulfonium trifluoromethanesulfonate, 1-
(4-Nitronaphthyl) diethylsulfonium nonafluoro-n-butanesulfonate 1- (4-nitronaphthyl) diethylsulfonium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophene Trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium per Fluoro-n-octane sulfonate, 1-
(4-Methoxynaphthyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxynaphthyl) tetrahydrothiophenium nonafluoro-
n-butanesulfonate, 1- (4-methoxynaphthyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-ethoxynaphthyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxynaphthyl) tetrahydro Thiophenium nonafluoro-n-butane sulfonate, 1
-(4-ethoxynaphthyl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4
-N-butoxynaphthyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthyl) tetrahydrothiophenium Perfluoro
n-octane sulfonate, diphenyl iodonium trifluoromethane sulfonate, diphenyl iodonium nonafluoro-n-butane sulfonate, diphenyl iodonium perfluoro-n-octane sulfonate, bis (4-t-butylphenyl) iodonium trifluoromethane sulfonate, bis (4-t -Butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, cyclohexyl-2-oxocyclohexyl-methylsulfonium trifluoromethanesulfonate, dicyclohexyl-
2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, and the like.

[2] Halogen-containing compound phenylbis (trichloromethyl) -s-triazine,
4-methoxyphenylbis (trichloromethyl) -s-
Triazine, 1-naphthylbis (trichloromethyl)-
(Trichloromethyl) -s-triazine derivatives such as s-triazine and 1,1-bis (4-chlorophenyl)-
2,2,2-trichloroethane and the like. [3] Diazoketone compound 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4 of 2,3,4,4'-tetrahydroxybenzophenone -Sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester and 1,1,1-tris (4-hydroxyphenyl) ethane 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2- Naphthoquinone diazide-5-sulfonic acid ester and the like. [4] Sulfone compound 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane and the like. [5] Sulfonic acid compound benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate) and nitrobenzyl-9,
10-diethoxyanthracene-2-sulfonate and the like.

Among these other radiation-sensitive acid generators (B), triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-). 4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-
(3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4-n-butoxynaphthyl) tetrahydrothiophenium nonafluoro-n-butane sulfonate, 1- (4 -N-butoxynaphthyl) tetrahydrothiophenium perfluoro-n-octane sulfonate, diphenyliodonium trifluoromethane sulfonate, diphenyliodonium nonafluoro-n-butane sulfonate, diphenyliodonium perfluoro-n-octane sulfonate, bis (4-t- Butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) io Donium perfluoro-n-octane sulfonate, cyclohexyl 2-oxocyclohexyl methyl sulfonium trifluoromethane sulfonate, dicyclohexyl 2-oxo cyclohexyl sulfonium trifluoro methane sulfonate, 2-oxo cyclohexyl dimethyl sulfonium trifluoro methane sulfonate is used for resist sensitivity and contrast. From the point of, it is preferable.

In the radiation-sensitive resin composition of the present invention, the total content of the acid generator (B) and the acid generator (b) is preferably 0.1 per 100 parts by weight of the resin (A). 1 to
20 parts by mass, more preferably 0.5 to 20 parts by mass, still more preferably 0.5 to 10 parts by mass. When the total content is 0.1 part by mass or more, it is possible to prevent deterioration of sensitivity and developability, while when it is 20 parts by mass or less, deterioration of transparency to radiation is prevented, A rectangular resist pattern is easily obtained, which is preferable. The content of the acid generator (b) is preferably 80% by mass or less, more preferably 70% by mass based on 100 parts by mass of the total content of the acid generator (B) and the acid generator (b). It is not more than 60% by mass, more preferably not more than 60% by mass. It is preferable to use the acid generator (b) in an amount of 80% by weight or less, because the desired effects of the present invention can be maintained and improved.

<3> Other Components An acid diffusion controller may be added to the radiation-sensitive resin composition of the present invention. The acid diffusion control agent has a function of controlling a diffusion phenomenon of an acid generated from the radiation-sensitive acid generator (B) upon exposure in the resist film and suppressing an unfavorable chemical reaction in a non-exposed region. Therefore,
By adding the above acid diffusion controller, the storage stability of the resulting radiation sensitive resin composition can be further improved. Further, by blending the above-mentioned acid diffusion control agent, the resolution as a resist can be further improved, and the change in the line width of the resist pattern due to the variation in the leaving time (PED) from exposure to development can be suppressed. As a result, a radiation-sensitive resin composition having extremely excellent process stability can be obtained, which is preferable.

As the acid diffusion control agent, a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment during the resist pattern forming step is preferable. Examples of the nitrogen-containing organic compound include compounds represented by the following general formula (4) (hereinafter referred to as "nitrogen-containing compound (a)"), compounds having two nitrogen atoms in the same molecule (hereinafter referred to as ""Nitrogen-containing compound (b)"), polyamino compound or polymer having three or more nitrogen atoms (hereinafter collectively referred to as "nitrogen-containing compound (c)"), amide group-containing compound, urea compound. And nitrogen-containing heterocyclic compounds. Then, of these nitrogen-containing organic compounds, the nitrogen-containing compound (a), the amide group-containing compound and the nitrogen-containing heterocyclic compound can be obtained as a resist having little dependency on the leaving time (PED) from exposure to development processing. It is preferable from the point. The acid diffusion control agent may be used alone or in combination of two or more.

[0043]

[Chemical 7]

In the above general formula (4), R ⁵ , R ⁶ and R ⁷
Are each independently a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group. Here, examples of the substituted or non-substituted linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and specifically, methyl group and ethyl group. Group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n- Heptyl group, n
-Octyl group, n-ethylhexyl group, n-nonyl group,
Examples thereof include n-decyl group. Examples of the substituted or unsubstituted aryl group include those having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group and a 1-naphthyl group. Further, examples of the substituted or unsubstituted aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms. Specifically, benzyl group, α-methylbenzyl group, phenethyl group, naphthylmethyl group and the like. Is mentioned. The above R
⁵ , R ⁶ and R ⁷ may be the same type of atom or substituent with each other, or may be different atoms or substituents.

The above-mentioned nitrogen-containing compound (a) is specifically
For example, n-hexylamine, n-heptylamine, n
-Octylamine, n-nonylamine, n-decylamine, cyclohexylamine and other mono (cyclo) alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine , Di-n-octylamine, di-n-nonylamine,
Di-n-decylamine, cyclohexylmethylamine,
Di (cyclo) alkylamines such as dicyclohexylamine; triethylamine, tri-n-propylamine,
Tri-n-butylamine, tri-n-pentylamine,
Tri (cyclo) such as tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine Alkylamines; aromatic amines such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine And the like.

Specific examples of the nitrogen-containing compound (b) include ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,
4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl)
Propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl)
-2- (3-hydroxyphenyl) propane, 2- (4
-Aminophenyl) -2- (4-hydroxyphenyl)
Propane, 1,4-bis [1- (4-aminophenyl)
-1-Methylethyl] benzene, 1,3-bis [1-
(4-aminophenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether and the like can be mentioned.

The nitrogen-containing compound (c) is specifically as follows.
For example, polyethyleneimine, polyallylamine, 2-
Examples thereof include polymers of dimethylaminoethyl acrylamide.

Specifically, the amide group-containing compound is
For example, Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, N- t-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-
Adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4 ′ -Diaminodiphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N, N'N'-tetra-t-butoxycarbonylhexamethylenediamine,
N, N'-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-t-butoxycarbonyl-1,8-diaminooctane, N, N'-di-t-butoxycarbonyl- 1,9-diaminononane, N, N'-
Di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12
-Diaminododecane, N, N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt
-Butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, N
In addition to Nt-butoxycarbonyl group-containing amino compounds such as -t-butoxycarbonyl-2-phenylbenzimidazole, formamide, N-methylformamide,
Examples thereof include N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone and N-methylpyrrolidone.

Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea,
Examples thereof include 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea and tri-n-butylthiourea.

The above-mentioned nitrogen-containing heterocyclic compound is specifically,
For example, imidazole, 4-methylimidazole, 4-
Imidazoles such as methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2
-Methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine and other pyridines; piperazine, 1- (2-hydroxyethyl) piperazine and other piperazines In addition, pyrazine, pyrazole, pyridazine, quinoxaline, purine, pyrrolidine, piperidine, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2. 2.2] Octane and the like can be mentioned.

Further, the radiation-sensitive resin composition of the present invention may contain an alicyclic additive having an acid dissociable group. The alicyclic additive having an acid dissociable group is a component that exhibits an effect of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. The addition of the alicyclic group having an acid dissociable group has the effect of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. Here, the “acid-dissociable group” is not particularly limited in its type and structure as long as it is a group in which the protective group is dissociated by the action of an acid to generate an alkali-soluble group. Examples of the acid dissociable group include groups that dissociate by the action of an acid to form a carboxyl group, a hydroxyl group, a sulfonic acid group and the like. In the present invention, the alicyclic additive having an acid dissociable group may be used alone or in combination of two or more.

The alicyclic additive is, for example, t-butyl 1-adamantanecarboxylate, t-butoxycarbonylmethyl 1-adamantanecarboxylate,
1,3-adamantanedicarboxylate di-t-butyl, 1,
-Adamantane derivatives such as t-butyl adamantane acetate, t-butoxycarbonylmethyl 1-adamantane acetate and di-t-butyl 1,3-adamantane diacetate; t-butyl deoxycholate, t-butoxycarbonylmethyl deoxycholate , Deoxycholic acid 2-ethoxyethyl, deoxycholic acid 2-cyclohexyloxyethyl, deoxycholic acid 3-oxocyclohexyl, deoxycholic acid tetrahydropyranyl, deoxycholic acid mevalonolactone ester, and other deoxycholic acid esters; lithocholic acid t-Butyl, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid, 2-cyclohexyloxyethyl lithocholic acid, 3-oxocyclohexyl lithocholic acid, tetrahydropyranic lithocholic acid , Mention may be made of lithocholic acid esters such as lithocholic mevalonolactone ester.

Further, the radiation-sensitive resin composition of the present invention may contain a surfactant. The surfactant exhibits an action of improving coating property, striation, developability and the like. When the surfactant is blended, the blending amount is usually 2 parts by mass or less, preferably 100 parts by mass with respect to the total of 100 parts by mass of the resin (A), the acid generator (B) and the acid generator (b). The amount is 1.5 parts by mass or less, more preferably 1 part by mass or less. The above surfactants may be used alone or in combination of two or more.

Examples of the above surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether,
In addition to nonionic surfactants such as polyethylene glycol dilaurate and polyethylene glycol distearate, KP341 (Shin-Etsu Chemical Co., Ltd.)
Manufactured), Polyflow No. 75, the same No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303,
EF352 (manufactured by Tochem Products Co., Ltd.), Megafax F171, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S. -382, same SC-101, same SC-10
2, the same SC-103, the same SC-104, the same SC-10
5, the same SC-106 (manufactured by Asahi Glass Co., Ltd.) and the like.

A sensitizer may be added to the radiation-sensitive resin composition of the present invention. The sensitizer has a function of absorbing the energy of radiation and transmitting the energy to the radiation-sensitive acid generator (B), thereby increasing the amount of acid produced. With such an action, the apparent sensitivity of the radiation-sensitive resin composition can be improved. The sensitizers may be used alone or in combination of two or more. Specific examples of the sensitizer include acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrene, anthracenes, phenothiazines and the like.

In the radiation-sensitive resin composition of the present invention, if necessary, one or two of the above-mentioned acid diffusion controller, an alicyclic additive having an acid dissociable group, a surfactant and a sensitizer. It is possible to mix one or more kinds. Further, other additives may be added within the range not impairing the object of the present invention. Examples of other compounding agents include dyes and pigments. By blending a dye or a pigment, the latent image in the exposed area can be visualized and the effect of halation during exposure can be mitigated. In addition, as other compounding agents, for example, an alkali-soluble resin described later, a low-molecular weight alkali solubility control agent having an acid dissociable protective group, an adhesion aid for improving the adhesion to a substrate, an antihalation agent Agents, storage stabilizers, defoamers and the like.

<4> Preparation of Radiation-Sensitive Resin Composition The radiation-sensitive resin composition of the present invention usually contains the resin (A), the radiation-sensitive acid generator (B) and other additive components as a solvent. To obtain a uniform solution, and then, if necessary, it is prepared by filtering with a filter having a pore size of about 0.2 μm. As the solvent of the present invention, a solvent containing at least one selected from the group consisting of propylene glycol monomethyl ether acetate, 2-heptanone and cyclohexanone is preferably used. It is preferable to use such a solvent because the in-plane uniformity of the film at the time of coating becomes good.

The above-mentioned solvent is a solvent other than propylene glycol monomethyl ether acetate, 2-heptanone and cyclohexanone (hereinafter, "other solvent").
Say. ) Can be included. Examples of the other solvent include the following solvents. [1] Propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n
-Butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate, and other propylene glycol monoalkyl ether acetates; [2] 2-butanone, 2-pentanone , 3-methyl-2
-Butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-octanone, or other linear or branched ketones; [3 ] Cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone and isophorone; [4] Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2 -N-propyl hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, t-hydroxypropionate t
Alkyl 2-hydroxypropionates such as butyl; [5] alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate Kinds; [6] n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol Mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl Ether,
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, toluene, xylene, 2-hydroxy Ethyl-2-methylpropionate,
Ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate,
3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethyl Formamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-
Octanol, 1-nonanol, benzyl alcohol,
Benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, etc .;

Of the above-mentioned other solvents, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, 2-hydroxypropionate alkyls, 3-alkoxypropionate alkyls, etc. It is preferable because the solubility of the resin is high.

The amount of the above-mentioned solvent used is such that the concentration of the total solid content in the homogeneous solution is usually 5 to 50% by mass, preferably 10 to 50% by mass.
50% by mass, further preferably 10 to 40% by mass, more preferably 10 to 30% by mass, particularly preferably 10 to 25%.
% By weight. It is preferable to set it in such a range since the in-plane uniformity of the film at the time of coating becomes good. When the solvent contains the other solvent, the amount of the other solvent used is usually 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less with respect to the total amount of the solvent. is there.

<5> Method for forming resist pattern The radiation-sensitive resin composition of the present invention is particularly useful as a chemically amplified resist. In the above chemically amplified resist,
Due to the action of the acid generated from the radiation-sensitive acid generator upon exposure, the protective group of the acid-dissociable group in the resin (A) is dissociated, etc., so that the solubility of the exposed portion of the resist in an alkaline developer is increased. . As a result, the exposed portion is dissolved and removed by the alkali developing solution, and a positive resist pattern can be obtained.

When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution is spin-coated,
A resist film is formed by applying it on a substrate such as a silicon wafer or a wafer covered with aluminum by an appropriate applying means such as cast coating or roll coating. And, if necessary, heat treatment (hereinafter,
It is called "PB". Then, the resist film is exposed to form a predetermined resist pattern. As the radiation used during the exposure, an actinic ray (visible ray, ultraviolet ray, far ultraviolet ray, X-ray, charged particle beam, etc.) is appropriately selected and used according to the type of the acid generator used. Among these, far ultraviolet rays and charged particle beams represented by ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm) are preferable from the viewpoint of the resolution of the resist, and ArF excimer laser is particularly preferable.

When forming a resist pattern from the radiation-sensitive resin composition of the present invention, a heat treatment after exposure (hereinafter, referred to as
It is called "PEB". Is preferable because the dissociation reaction of the acid dissociable group in the resin (A) smoothly proceeds. The heating condition of the PEB varies depending on the composition of the radiation-sensitive resin composition, but is usually 30 to 200 ° C, preferably 50 to 170 ° C.

In forming a resist pattern from the radiation-sensitive resin composition of the present invention, in order to maximize the potential of the radiation-sensitive resin composition, for example, Japanese Patent Publication No. 6-
As disclosed in Japanese Patent No. 12452 and the like, an organic or inorganic antireflection film may be formed on the substrate used. In order to prevent the influence of basic impurities contained in the environmental atmosphere, for example, Japanese Patent Laid-Open No. 5-1
As disclosed in JP-A-88598, a protective film may be provided on the resist film. Furthermore, these techniques can be used together.

Then, the exposed resist film is developed to form a predetermined resist pattern. Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine and di-n-.
Propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine,
Tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.
4.0] -7-Undecene, 1,5-diazabicyclo-
An alkaline aqueous solution in which at least one kind of alkaline compound such as [4.3.0] -5-nonene is dissolved is preferable.

Further, for example, an organic solvent can be added to the developer containing the above alkaline aqueous solution. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone,
Cyclohexanone, 3-methylcyclopentanone, 2,
Ketones such as 6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol,
Alcohols such as t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; ethyl acetate, acetic acid n-
Examples thereof include esters such as butyl and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; and phenol, acetonylacetone, and dimethylformamide. The above organic solvents may be used alone, or
You may use 2 or more types together.

The concentration of the alkaline aqueous solution is usually 1
It is 0% by weight or less. In this case, if the concentration of the alkaline aqueous solution exceeds 10% by weight, the unexposed area may be dissolved in the developing solution, which is not preferable. When the organic solvent is added to the developer containing the alkaline aqueous solution, the amount of the organic solvent used is 10 with respect to the alkaline aqueous solution.
It is preferably 0% by volume or less. In this case, if the amount of the organic solvent used exceeds 100% by volume, the developability may be deteriorated and the undeveloped portion in the exposed area may increase.

Further, a proper amount of a surfactant or the like can be added to the developer containing the above alkaline aqueous solution. This is preferable because the wettability of the developer with respect to the resist can be improved. Incidentally, after developing with a developer containing an alkaline aqueous solution, it is generally washed with water and dried.

[0069]

EXAMPLES Examples of the present invention will be shown below to more specifically explain the embodiments of the present invention. However, the present invention is
There is no limitation to these examples. Also,
Here, “part” is based on weight unless otherwise specified.

(1) Synthesis of Resins (A-1) to (A-4) and Comparative Resin (R-1) Resins (A-1) to (A-4) and Comparative Resin (R-1) were prepared by the following method. The resin (R-1) was synthesized. The resin (A
-1) to (A-4) and Mw of comparative resin (R-1)
Is a GPC column manufactured by Tosoh Corporation (G2000HXL
2 pieces, G3000HXL 1 piece, G4000HXL
1), a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C. under analysis conditions,
It was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard.

Resin (A-1) The above general formula (5-1) (provided that R ¹ = methyl group, R ² =
42.69 g (40 mol%) of the compound represented by the ethyl group) and 57.31 of the compound represented by the chemical formula (3).
g (60 mol%) and methyl azobisisovalerate 6.0
0 g was dissolved in 200 g of 2-butanone to prepare a monomer solution as a uniform solution. And 2-butanone 100
A 1000 ml three-necked flask charged with g was purged with nitrogen for 30 minutes. After purging with nitrogen, the inside of the flask was heated to 80 ° C. with stirring, and the above-prepared monomer solution was added dropwise at a rate of 10 ml / 5 min using a dropping funnel. Polymerization was carried out for 5 hours, with the start of dropping being the start of polymerization. After the polymerization is completed, the reaction solution is cooled to 30 ° C or lower,
Then, the reaction solution was poured into 2000 g of methanol,
The white powder deposited was filtered off. The white powder separated by filtration was mixed with 400 g of methanol and stirred as a slurry, and the operation was repeated twice to wash, then, filtered and filtered at 50 ° C.
After drying for an hour, a white powder of resin (A-1) was obtained (69
g, yield 69% by weight). The resin (A-1) has an Mw of 65.
Of the repeating unit represented by the general formula (1-1) (wherein R ¹ = methyl group, R ² = ethyl group) and the repeating unit derived from the compound represented by the chemical formula (3). It was a copolymer with a content of 39.1: 60.9 (mol%).

Resin (A-2) The above general formula (5-2) (wherein R ¹ = methyl group, R ² =
26.01 g (30 mol%) of a compound represented by ethyl group) and the above general formula (5-5) (wherein R ¹ = methyl group).
10.57 g (10 mol%) of the compound represented by the formula (6), 63.42 g (60 mol%) of the compound represented by the chemical formula (3) and 6.00 g of methyl azobisisovalerate were dissolved in 200 g of 2-butanone, and homogeneous. A resin (A-2) was obtained as a white powder in the same manner as in the synthesis of the resin (A-1) except that the monomer solution was used as a solution (73 g, yield 7).
3% by weight). The resin (A-2) has an Mw of 7200 and has the above general formula (1-2) (provided that R ¹ = methyl group, R
² = ethyl group), a repeating unit represented by the above formula (1-
5) (however, the content of the repeating unit represented by R ¹ = methyl group) and the repeating unit derived from the compound represented by the chemical formula (3) is 29.9: 9.9: 60.2 (mole). %) Copolymer.

Resin (A-3) The above general formula (5-3) (provided that R ¹ = methyl group, R ² =
37.06 g (40 mol%) of a compound represented by the ethyl group) and 62.94 g of a compound represented by the above chemical formula (3)
(60 mol%) and methyl azobisisovalerate 6.00
Resin (A-3) was obtained as a white powder (78) in the same manner as in the synthesis of the above resin (A-1) except that 200 g of 2-butanone was dissolved and a monomer solution was used as a uniform solution.
g, yield 78% by weight). The resin (A-3) has an Mw of 76.
Of the repeating unit represented by the general formula (1-3) (wherein R ¹ = methyl group, R ² = ethyl group) and the repeating unit derived from the compound represented by the chemical formula (3). It was a copolymer with a content of 39.2: 60.8 (mol%).

Resin (A-4) The above general formula (5-4) (provided that R ¹ = methyl group, R ² =
42.44 g (40 mol%) of a compound represented by the ethyl group) and 47.47 g of a compound represented by the above chemical formula (3)
(50 mol%), 3-hydroxy-1-adamantyl methacrylate 10.09 g (10 mol%) and methyl azobisisovalerate 6.00 g were dissolved in 2-butanone 200 g, except that a monomer solution was used as a uniform solution. ,
A white powder resin (A-4) was obtained in the same manner as in the synthesis of the resin (A-1) (75 g, yield 75% by weight). The resin (A-4) has Mw of 7300, and has the above general formula (1
-4) (provided that R ¹ = methyl group, R ² = ethyl group), a repeating unit derived from the compound represented by the chemical formula (3) and 3-hydroxy-1-adamantyl methacrylate. The content of the repeating unit derived from the copolymer was 39.5: 50.6: 9.9 (mol%).

Comparative resin (R-1) 2-methacrylic acid 2-methyl-adamantan-2-yl ester 41.28 g (40 mol%), 58.72 g (60 mol) of the compound represented by the above chemical formula (3). %) And 6.00 g of methyl azobisisovalerate in 200 g of 2-butanone, and using a monomer solution which was made into a uniform solution, in the same manner as in the synthesis of the above resin (A-1), for comparison of white powder. Resin (R-1) was obtained (76 g, yield 7).
6% by weight). Comparative resin (R-1) has Mw of 7500
And 2-methyl methacrylate 2-adamantane-
The content of the repeating unit derived from 2-yl ester and the repeating unit derived from the compound represented by the chemical formula (3) was 39.5: 60.5 (mol%), and the copolymer was obtained.

(2) Preparation of radiation-sensitive resin composition The above resins (A-1) to (A-4) and the comparative resin (R-
1), the following acid generator (B), solvent (C) and acid diffusion control agent (D) were used in the proportions shown in Table 1, and Examples 1 to 1 were used.
The radiation-sensitive resin compositions of 6 and Comparative Example 1 were prepared. still,
The numbers in parentheses in Table 1 represent "parts".

Radiation-sensitive acid generator (B) B-1: N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] heptane-2,3-dicarboximide B-2: N -(Trifluoromethylsulfonyloxy)
-1,2-Cyclohexanedicarboximide B-3: N- (trifluoromethylsulfonyloxy)
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide B'-1: Triphenylsulfonium trifluoromethanesulfonate solvent (C) C-1: Propylene glycol monomethyl ether acetate C-2: 2 -Heptanoic acid diffusion controller (D) D-1: Nt-butoxycarbonyl-2-phenylbenzimidazole

[0078]

[Table 1]

(3) Performance Evaluation The performance of each radiation-sensitive resin composition solution of Examples 1 to 6 and Comparative Example was evaluated by the following method. The results are shown in Table 2 below. Radiation Transmittance (%) Each of the radiation-sensitive resin compositions of Examples 1 to 6 and Comparative Example was applied onto quartz glass by spin coating, and then Table 2
As shown in, a PB was performed for 90 seconds on a hot plate kept at 110 ° C. or 130 ° C. to form a resist film having a film thickness of 0.34 μm. Then, with respect to this resist film, the radiation transmittance (%) was calculated from the absorbance at a wavelength of 193 nm, and used as a measure of transparency in the deep ultraviolet region.

Sensitivity (J / m ² ) As a substrate, AR with a film thickness of 820 Å was formed on the surface.
A silicone wafer on which C25 (manufactured by Brewer) was formed was used. Then, each of the radiation-sensitive resin compositions of Examples 1 to 6 and Comparative Example was applied onto the above-mentioned substrate by spin coating, and then, as shown in Table 2, at 110 ° C or 13 ° C.
PB was performed for 90 seconds on a hot plate kept at 0 ° C. to form a resist film having a film thickness of 0.34 μm. Then, ArF excimer laser exposure device manufactured by Nikon Corporation (lens numerical aperture 0.55, exposure wavelength 193 nm, A in the table)
rF) and Nikon Stepper NSR220
5 EX12B (numerical aperture 0.55, exposure wavelength 24
8 nm, described as KrF in the table), through a mask pattern, or by a simple electron beam drawing device (manufactured by Hitachi, model "HL700D-M", output; 50 Kev, current density;
The resist coating was irradiated by direct writing of 4.5 amps, noted EB in the table). Then, as shown in Table 2, PEB was performed for 90 seconds on a hot plate kept at 100 ° C. or 130 ° C., and then developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 1 minute. After the development, the resist film was washed with water and dried to form a positive resist pattern. At this time, the dose for forming a line-and-space pattern (1L1S) having a line width of 0.16 μm in a line width of 1: 1 was taken as the optimum dose, and this optimum dose was taken as the sensitivity.

Resolution (μm) The minimum dimension of the resist pattern that can be resolved at the optimum dose was determined as the resolution (μm).

Dry Etching Resistance Each of the radiation sensitive resin compositions of Examples 1 to 6 and Comparative Example was applied onto a silicone wafer by spin coating and dried to form a resist film having a thickness of 0.5 μm. Then, a dry etching device manufactured by PMT (“Pinnac
le8000 ″), the etching gas was CF ₄ , the gas flow rate was 75 sccm, the pressure was 332.5 mPa, and the output was 2500 W, and the resist film was dry-etched to measure the etching rate. Then, the relative etching rate was determined with the etching rate of the resist film formed from the radiation-sensitive resin composition of the comparative example being 1.0, and this was taken as the value of dry etching resistance. The smaller this value, the better the dry etching resistance.

Pattern shape A line-and-space pattern (1L1S) having a line width of 0.16 μm is measured with a scanning electron microscope to measure the lower side dimension L1 and the upper and lower side dimension L2 of 0.85 ≦ L.
When 2 / L1 ≦ 1 was satisfied and the pattern shape was not trailing, the pattern shape was evaluated as “good”.

[0084]

[Table 2]

(4) Effects of Examples Each of the radiation-sensitive resin compositions of Examples 1 to 6 containing the resin (A) and the radiation-sensitive acid generator (B) of the present invention has a pattern shape. In addition to being excellent, the radiation transmittance (wavelength 193 nm) is 72 to 75%, and the sensitivity (wavelength 193).
nm) is 125 to 146 J / m ² , dry etching resistance is 0.9 to 1.0, and resolution is 0.13 to 0.1.
The value is as small as 4 μm. On the other hand, in Comparative Example 1 in which the radiation-sensitive acid generator (B) of the present invention was not used, PB
Of 110 ° C. and PEB of 100 ° C., the pattern shape cannot be resolved and the radiation transmittance at a wavelength of 193 nm is 60.
% Is low. Further, in Comparative Example 1, PB and PEB were heated to 130 ° C.
In the case of, the pattern shape becomes a forward taper (trapezoidal shape) although it is resolved, the pattern shape is worse than in Examples 1 to 6, and the radiation transmittance at a wavelength of 193 nm is 60%. It turns out that it is lower than ~ 6.
From the above, it is understood that the radiation-sensitive resin composition of the present invention has high transparency to radiation and is excellent in basic physical properties as a resist such as sensitivity, resolution, dry etching resistance and pattern shape.

Continued front page    (72) Inventor Tsutomu Shimokawa             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. (72) Inventor Yukio Nishimura             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. (72) Inventor Isao Nishimura             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F term (reference) 2H025 AA01 AA02 AA03 AA09 AB16                       AC04 AC08 AD03                 4J100 AL08P AL08Q AL08R AL08S                       BC03P BC03S BC04P BC04S                       BC08P BC08S BC09P BC09R                       BC09S BC12P BC12S BC53Q                       CA04 CA05 CA06 JA37

Claims (3)

[Claims] 1. A repeating unit represented by the following general formula (1-
1) to (1-5), the acid-labile group-containing resin (A) containing at least one of the repeating units represented by the formulas (1) to (1-5), and the radiation-sensitive acid generator represented by the following general formula (2) ( B), and a radiation-sensitive resin composition comprising: [Chemical 1] [Chemical 2] [In the general formula (1-1) ~ (1-5), R 1 represents a hydrogen atom or a methyl group independently of one another, ^{R 2} is an alkyl group having 2 to 6 carbon atoms independently of one another. In addition, in the general formula (2), R ³ represents a monovalent organic group, and R ⁴ represents a divalent organic group. ] 2. The above general formulas (1-1) to (1) in 100 mol% of all repeating units of the acid-dissociable group-containing resin (A).
The total content of repeating units represented by -5) is 5 to 5
The radiation-sensitive resin composition according to claim 1, which is 0 mol%. 3. In the general formulas (1-1) to (1-4),
The radiation-sensitive resin composition according to claim 1, wherein R ² is an ethyl group.