JP2003330196A - Radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition having high transparency at ≤193 nm wavelength and excellent basic physical properties as a resist such as resolution or the like and suitable as a chemically amplifying resist. <P>SOLUTION: The radiation-sensitive resin composition contains (A) an acid dissociable group-containing resin such as a resin having a repeating unit expressed by formula (a-1) and/or a repeating unit expressed by formula (a-2) and a repeating unit expressed by formula (b-1) and/or a repeating unit expressed by formula (b-2) and (B) a radiation-sensitive acid generating agent which generates an acid, typified as trifluoromethanesulfonic acid, nonafluoro-n- butanesulfonic acid, 2-(2-norbornyl)-1,1,2,2-tetrafluoroethanesulfonic acid, or the like. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a radiation-sensitive resin composition, more specifically, far ultraviolet rays such as F ₂ excimer laser, ArF excimer laser and KrF excimer laser, charged particles such as electron beam and X-ray. The present invention relates to a radiation-sensitive resin composition which 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 In recent years, demands for higher density and higher integration of LSIs (highly integrated circuits) have increased more and more, and along with this, miniaturization of wiring patterns has been rapidly progressing. As one of means for dealing with such miniaturization of wiring patterns, there is a method of shortening the wavelength of radiation used in a lithography process, and in recent years, g-line (wavelength 436 nm)
Ultraviolet rays such as F ₂ excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm), electron rays, X-rays, etc. Is being used. As a resist suitable for such short-wavelength radiation, a component having an acid-dissociable functional group and a chemical amplification effect of a radiation-sensitive acid generator that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”) The resist used (hereinafter, "chemically amplified resist")
Say. ) Have been proposed. By the way, novolak resins, poly (vinylphenol), etc. have been used as resin components in conventional chemically amplified resists.
Even if these materials have an aromatic ring in their structure and have excellent dry etching resistance, they have strong absorption at a wavelength of 193 nm. Therefore, for example, in a lithography process using an ArF excimer laser, high sensitivity, high resolution, and high High accuracy corresponding to the aspect ratio cannot be obtained. Therefore, it is transparent to a wavelength of 193 nm or less, particularly F ₂ excimer laser (wavelength 157 nm), Kr ₂ excimer laser (wavelength 147 nm), ArKr excimer laser (wavelength 134 nm), etc. There is a demand for a resist resin material having etching resistance.

The applicant of the present invention has already proposed, as a resin component of a chemically amplified resist having excellent transparency at a wavelength of 193 nm or less and good dry etching resistance, a copolymer of a norbornene derivative and another unsaturated compound. A resin having an alicyclic skeleton in its main chain has been proposed (JP-A-10-11156).
No. 9). On the other hand, as a general fluorine-containing resin, Daikin Industries, Ltd. has reported a fluorine-containing norbornene-based copolymer of a norbornene-based compound and fluorinated ethylenes (see WO91 / 00880),
In addition to alcoholic hydroxyl groups and carboxyl groups,
Hexafluoroalcohol residue (eg hydroxyhexafluoropropyl group), which is considered to be a promising functional group in resin components of today's chemically amplified resists.
Is being considered.

In addition, E-Dupont de Nemours Co., Ltd. has reported that the above-mentioned fluorine-containing norbornene-based copolymer is used as a resin component of a chemically amplified resist (see WO00 / 17712). There, it is described that the transmittance is high at a wavelength of 365 nm or less. However, the data of the transmittance at a wavelength of 365 nm or less are not specifically shown,
The performance as a chemically amplified resist is not always clear. Further, the company has proposed a chemically amplified resist using a fluorine-containing norbornene-based copolymer having a fluoroalcohol residue introduced therein (WO / 0067).
072), particularly the transmittance at a wavelength of 157 nm has not been examined, and no resist showing good performance at the wavelength has been found. Further, Asahi Glass Co., Ltd. has proposed a resin synthesized by cyclopolymerization of fluorinated olefins, which contains a ring structure in the main chain and has a halogen atom in the polymer main chain on the ring or other than the ring ( U.S. Pat. No. 4,910,276), where the use of the resin in resist materials is not considered.

Further, in the chemically amplified resist,
It is known that the radiation-sensitive acid generator has a great influence on the resist performance. Today, onium salt compounds are widely used because of their high quantum yield of acid generation by exposure and high sensitivity. However, it is difficult to predict the action because it is intricately related to the main chain structure and / or side chain structure of the resin component, functional groups, etc., and it is difficult to generate a radiation-sensitive acid suitable for the selected resin component. Finding a drug is still difficult. Under such circumstances, from the viewpoint of technological development that can respond to the progress of miniaturization in highly integrated circuit devices, the transparency is high at a wavelength of 193 nm or less, especially at 157 nm, and the basic physical properties as a resist such as resolution are excellent. There is a strong demand for chemically amplified resists.

[0006]

The object of the present invention is to suitably use as a chemically amplified resist having a high transparency at a wavelength of 193 nm or less, particularly 157 nm or less, and excellent basic physical properties as a resist such as resolution. It is intended to provide a radiation-sensitive resin composition capable of

[0007]

According to the present invention, the above-mentioned problems are protected by (A) an alkali-insoluble or sparingly-soluble acid-dissociable protective group having a repeating unit represented by the following general formula (1). Resin which becomes alkali-soluble by the action of an acid, and (B) a radiation-sensitive acid generator which generates trifluoromethanesulfonic acid or an acid represented by the following general formula (I) upon irradiation with radiation. It is achieved by a radiation-sensitive resin composition comprising:

[0008]

[Chemical 8] [In the general formula (1), each R ¹ is independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkyl group having 1 to 10 carbon atoms. Of the fluorinated alkyl group, each A independently represents -O- or a group represented by the following formula (2), and at least two A are groups represented by the formula (2):
m and n are 0 or 1, respectively, and (m + n) = 1.

[0009]

[Chemical 9] (In the formula, each R ² is independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched fluorine atom having 1 to 10 carbon atoms. Alkyl group or a monovalent group which is dissociated by an acid to form a hydroxyl group.)]

[0010]

[Chemical 10] [In the general formula (I), Ra is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 20 carbon atoms, A cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms or a cyclic monovalent fluorinated hydrocarbon group having 3 to 20 carbon atoms is shown, and the monovalent hydrocarbon group and the monovalent fluorinated carbon group are shown. The hydrogen group may be substituted, and each Rb independently represents a fluorine atom or a trifluoromethyl group. ]

The present invention will be described in detail below. Resin (A) The component (A) in the present invention is an alkali-insoluble or alkali-insoluble acid dissociative agent having a repeating unit represented by the general formula (1) (hereinafter referred to as “repeating unit (1)”). A resin protected by a protecting group, which becomes alkali-soluble by the action of an acid (hereinafter referred to as "resin (A)").
Say. ) Consists of. The term "alkali-insoluble or sparingly alkali-soluble" as used herein means that under the alkaline developing conditions adopted when forming a resist pattern from a resist coating formed from a radiation-sensitive resin composition containing a resin (A), When a film using only the resin (A) instead of the resist film is developed, the initial film thickness of the film is 50
% Means the property that remains after development.

In the general formula (1), examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these halogen atoms, the fluorine atom is preferable. Examples of the linear or branched alkyl group having 1 to 10 carbon atoms of R ¹ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group. , S
ec-butyl group, t-butyl group, n-pentyl group, n-
Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like can be mentioned. Of these alkyl groups, a methyl group is particularly preferable.

Examples of the linear or branched fluorinated alkyl group having 1 to 10 carbon atoms represented by R ¹ include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group and heptafluoro. -N
-Propyl group, heptafluoro-i-propyl group, nonafluoro-n-butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, perfluoro-n
-Heptyl group, perfluoro-n-octyl group, perfluoro-n-nonyl group, perfluoro-n-decyl group and the like can be mentioned. Among these fluorinated alkyl groups, a trifluoromethyl group is particularly preferable.

R ¹ in the general formula (1) is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or the like.

In the group represented by the above formula (2) representing A (hereinafter, referred to as "linking group (2)"), a halogen atom of R ² or a straight or branched chain having 1 to 10 carbon atoms. Examples of the alkyl group and the linear or branched fluorinated alkyl group having 1 to 10 carbon atoms include the corresponding groups exemplified for R ¹ .

As the monovalent group which is dissociated by the acid of R ² and becomes a hydroxyl group, for example, a group represented by the following general formula (iii) can be mentioned.

[0017]

[Chemical 11] [In the general formula (iii), R ⁵ represents a monovalent group which is dissociated by an acid to generate a hydrogen atom. ]

In the general formula (iii), examples of the monovalent group (hereinafter referred to as “acid dissociable protecting group”) which is dissociated by the acid of R ⁵ to generate a hydrogen atom include, for example, t-butoxycarbonyl group, Methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, 9-fluorenylmethylcarbonyl group, 2,2,2-trichloroethylcarbonyl group, 2- (trimethylsilyl) ethylcarbonyl group, i-butylcarbonyl group, vinyl Organic carbonyl groups such as carbonyl group, allylcarbonyl group, benzylcarbonyl group, 4-ethoxy-1-naphthylcarbonyl group and methyldithiocarbonyl group;

Methoxymethyl group, methylthiomethyl group,
Ethoxymethyl group, ethylthiomethyl group, t-butoxymethyl group, t-butylthiomethyl group, (phenyldimethylsilyl) methoxymethyl group, benzyloxymethyl group,
t-butoxymethyl group, siloxymethyl group, 2-methoxyethoxymethyl group, 2,2,2-trichloroethoxymethyl group, bis (2-chloroethoxy) methyl group, 2-
(Trimethylsilyl) ethoxymethyl group, 1-methoxycyclohexyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 1-methoxyethyl group, 1- Ethoxyethyl group, 1- (2-chloroethoxy) ethyl group, 1-methyl-1-methoxyethyl group, 1-methyl-1-benzyloxyethyl group, 1- (2-chloroethoxy) ethyl group, 1
-Methyl-1-benzyloxy-2-fluoroethyl group,
2,2,2-trichloroethyl group, 2-trimethylsilylethyl group, 2- (phenylselenyl) ethyl group,
An organic group which forms an acetal structure by combining with an oxygen atom in the general formula (iii);

Trimethylsilyl group, triethylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, dimethylethylsilyl group, t-butyldimethylsilyl group, t
-Butyldiphenylsilyl group, tribenzylsilyl group,
Tri-p-xylylsilyl group, triphenylsilyl group,
Alkylsilyl groups such as diphenylmethylsilyl group and t-butylmethoxyphenylsilyl group; 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 2-
Examples of the alkyl-substituted alicyclic group such as methyl-2-norbornyl group, 2-ethyl-2-norbornyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group and 1-ethylcyclohexyl group. be able to.

Among these acid dissociable protective groups, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, t
-Butyldimethylsilyl group and the like are preferable.

R ² in the linking group (2) is preferably a hydrogen atom, a fluorine atom, a hydroxyl group, a methyl group, a trifluoromethyl group, a t-butoxycarbonyloxy group, a methoxymethoxy group, an ethoxymethoxy group or the like.

In the resin (A), the repeating unit (1) has only n = 0 (m = 1) or n = 1 (m =
N = 0 (m =
It is preferable that the repeating unit (1) of 1) and the repeating unit (1) of n = 1 (m = 0) coexist.

Further, the repeating unit (1) in the resin (A) is preferably a unit in which all three A are linking groups (2). In this case, the structure of the linking group (2) is acid dissociated. In the repeating unit (1) having no sex protecting group, it is preferable that only one of the linking groups (2) has one hydroxyl group and the remaining linking group (2) has no hydroxyl group, In the repeating unit (1) having an acid dissociable protective group, only one of the linking groups (2) is 1
It is preferable to have one acid-dissociable protective group, and the remaining linking group (2) has no hydroxyl group or acid-dissociable protective group.

The repeating unit (1) is represented by the following general formula (7)
Is a unit formed by cyclopolymerization of a diolefin-based monomer represented by (hereinafter referred to as “monomer (7)”).

[0026]

[Chemical 12]

When the compound of the following formula (7-1) is used as the monomer (7), the repeating unit (1) formed by the cyclopolymerization thereof is generally the following formula (8-1) or the formula (8) 8
-2).

[0028]

[Chemical 13] [Wherein, x and y are the number of each repeating unit, and x ≧
0, y ≧ 0, and (x + y)> 0 is satisfied. In the resin (A), the repeating unit (1) may be used alone or in combination of two or more.

The resin (A) is a repeating unit other than the repeating unit (1) (hereinafter referred to as "other repeating unit").
Can have one or more. Examples of the other repeating unit include repeating units in which only a part of each R ¹ in the general formula (1) is independently a hydroxyl group or a carboxyl group, two repeating units in the group A in the general formula (1). Examples thereof include a repeating unit in which at least one of R ² is a carboxyl group, and a repeating unit in which a hydrogen atom of a hydroxyl group or a carboxyl group in these repeating units is substituted with the acid dissociable protective group. Examples of the acid dissociable protective group in the other repeating unit include methoxymethyl group, ethoxymethyl group, t-butyl group, tetrahydropyranyl group, tetrahydrofuranyl group, 2-methyl-2-
The adamantyl group and the like are preferable.

The resin (A) has a fluorine content in its structure of preferably 30% by weight or more, more preferably 40% by weight or more, and particularly preferably 50% by weight or more.

In the resin (A), the content of the repeating unit having an acid dissociable protective group is usually 5 to 50 mol%, preferably 10 to 30 mol% based on all repeating units. In this case, if the content of the repeating unit having an acid dissociable protective group is less than 5 mol%, the residual film rate and resolution when used as a resist tend to be lowered, while if it exceeds 50 mol%, the resist is used. At this time, the sensitivity tends to decrease, and the pattern shape tends to be impaired. In addition, the rate of protection by the acid dissociable protective group in the resin (A) (the ratio of the group protected by the acid dissociable protective group to the total amount of the free hydroxyl group, the free carboxyl group and the group protected by the acid dissociable protective group) Is preferably 10 to 50 mol%,
It is particularly preferably 20 to 30 mol%.

The cyclopolymerization for producing the resin (A) is, for example, radical polymerization of a monomer corresponding to each repeating unit of hydroperoxides, dialkylperoxides, diacylperoxides, azo compounds and the like. It can be carried out by polymerizing using an initiator, if necessary, in the presence of a chain transfer agent, in the absence of a solvent or in a solvent. Examples of the solvent used for the polymerization include n
Alkanes such as -pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane; cyclohexane, cycloheptane, cyclooctane, decalin,
Cycloalkanes such as norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, fluorochloroethanes, hexamethylene dibromide and chlorobenzene Kind;
Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; ketones such as 2-butanone, 4-methyl-2-pentanone and 2-heptanone; tetrahydrofuran, dimethoxyethane, Examples thereof include ethers such as diethoxyethanes. These solvents may be used alone or in admixture of two or more.

The polystyrene equivalent weight average molecular weight (hereinafter referred to as "Mw") of the resin (A) by gel permeation chromatography (GPC) is usually 2,000.
0-100,000, preferably 5,000-50,0
00. In this case, the Mw of the resin (A) is 2,000.
If it is less than 100%, the heat resistance of the resulting resist tends to decrease, whereas if it exceeds 100,000, the developability of the resist tends to decrease. The ratio (Mw / Mn) of the Mw of the resin (A) and the polystyrene reduced number average molecular weight (hereinafter referred to as “Mn”) by gel permeation chromatography (GPC) is usually 1 to 5, preferably 1. ~ 3. The resin (A) is more preferable as it contains less impurities such as halogen and metal, whereby the sensitivity, resolution, process stability, pattern shape and the like when used as a resist can be further improved. Examples of the purification method of the resin (A) include:
Examples thereof include chemical purification methods such as washing with water and liquid extraction, and combinations of these chemical purification methods with physical purification methods such as ultrafiltration and centrifugation.

Acid Generator (B) The component (B) in the present invention is trifluoromethanesulfonic acid or the acid represented by the general formula (I) (hereinafter, referred to as the following, by exposure to deep ultraviolet rays, electron beams, X-rays, etc. Radiation-sensitive acid generator (hereinafter referred to as "acid generator (B1)") that generates "acid (I)" as an essential component (hereinafter referred to as "acid generator (B)") .).

In the general formula (I), Ra has 1 to 1 carbon atoms.
Examples of the linear or branched alkyl group of 20 include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group. , N-pentyl group, n-hexyl group,
Examples thereof include n-heptyl group and n-octyl group.

Examples of the linear or branched fluorinated alkyl group of Ra having 1 to 20 carbon atoms include, for example, trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group and heptafluoro- group. i-propyl group, nonafluoro-n-butyl group, nonafluoro-
i-butyl group, nonafluoro-sec-butyl group, nonafluoro-t-butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, perfluoro-n
Examples include -heptyl group and perfluoro-n-octyl group.

Further, as the cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms of Ra or the cyclic monovalent fluorinated hydrocarbon group having 3 to 20 carbon atoms or a substituted derivative thereof,
Examples thereof include groups represented by general formulas (α-1) to (α-7) shown below.

[0038]

[Chemical 14]

[0039]

[Chemical 15]

[0040]

[Chemical 16]

[0041]

[Chemical 17]

[0042]

[Chemical 18]

[0043]

[Chemical 19]

[0044]

[Chemical 20]

[In the general formulas (α-1) to (α-7), each R ⁶ is independently a hydrogen atom, a halogen atom, a hydroxyl group,
Acetyl group, carboxyl group, nitro group, cyano group, 1
Primary amino group, secondary amino group, linear or branched alkoxyl group having 1 to 10 carbon atoms, linear or branched alkyl group having 1 to 10 carbon atoms, or linear chain having 1 to 10 carbon atoms Or, a branched fluorinated alkyl group is shown, and each R ⁷ is independently a hydrogen atom, a halogen atom, or 1 to 10
A linear or branched alkyl group having 1 to 10 carbon atoms
Represents a linear or branched fluorinated alkyl group of
j is an integer of 0-10. In the general formula (α-4),
k is an integer of 1-18. In the general formula (α-5),
s is an integer of 0-3. ]

The preferred acid (I) in the present invention is, for example, heptafluoro-n-propanesulfonic acid, nonafluoro-n-butanesulfonic acid, perfluoro-n-octanesulfonic acid, 1,1,2,2,2. -Tetrafluoro-n-propanesulfonic acid, 1,1,2,
2, -tetrafluoro-n-butanesulfonic acid, 1,
1,2,2, -tetrafluoro-n-octane sulfonic acid,

On the bonds of the groups represented by the general formulas (α-1) to (α-7), --CF ₂ CF ₂ SO ₃ H and --CF ₂ CF are attached.
_{(CF 3) SO 3 H,} -CF (CF 3) CF 2 SO 3 H, -
_{CF (CF 3) CF (CF} 3) SO 3 H, -C (CF 3) 2 C
F ₂ SO ₃ H or _{-CF 2 C (CF 3) 2} SO 3 acid H groups attached thereto, for example, a acid of the formula (I-1) ~ (I -10).

[0048]

[Chemical 21]

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

[0051]

[Chemical formula 24]

[0052]

[Chemical 25]

In the present invention, the acid generator (B1) may be used alone or in combination of two or more kinds.
In the present invention, one or more other radiation-sensitive acid generators may be used in combination with the acid generator (B1), if necessary. As other preferable radiation-sensitive acid generator,
Upon exposure, for example, an acid represented by the following general formula (II) (hereinafter referred to as “acid (II)”), an acid represented by the following general formula (III) (hereinafter referred to as “acid (III)”) ) Or a compound represented by the following general formula (IV) (hereinafter referred to as “acid (IV)”) (hereinafter referred to as “acid generator (B2)”).
Say. ) Can be mentioned.

[0054]

[Chemical formula 26] [In the general formula (II), Rb represents a fluorine atom or a trifluoromethyl group, Rb 'represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and Rc
Is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms or a cyclic monovalent fluorinated hydrocarbon having 3 to 20 carbon atoms. Represents a group, and the monovalent hydrocarbon group and the monovalent fluorinated hydrocarbon group may be substituted.

In the general formula (III), Rd has 1 to 1 carbon atoms.
A linear or branched alkyl group having 20 carbon atoms or a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms is shown, and the monovalent hydrocarbon group may be substituted.

In the general formula (IV), Re is a carbon number of 1 to
20 linear or branched alkyl groups, having 1 to 1 carbon atoms
20 linear or branched fluorinated alkyl group, C 3-20 cyclic monovalent hydrocarbon group or C 3
To 20 cyclic monovalent fluorinated hydrocarbon groups,
The monovalent hydrocarbon group and the monovalent fluorinated hydrocarbon group may be substituted. ]

In the general formulas (II) to (IV), Rc and R
d and Re, a straight-chain or branched alkyl group having 1 to 20 carbon atoms, a straight-chain or branched fluorinated alkyl group having 1 to 20 carbon atoms, and optionally substituted 3 carbon atoms
As the cyclic monovalent hydrocarbon group of -20 and the cyclic monovalent fluorinated hydrocarbon group of 3 to 20 carbon atoms which may be substituted, for example, Ra in the general formula (I) is exemplified. The respective corresponding groups can be mentioned.

The preferred acid (II) is, for example, 1-
Fluoroethanesulfonic acid, 1-fluoro-n-propanesulfonic acid, 1-fluoro-n-butanesulfonic acid,
1-fluoro-n-octanesulfonic acid, 1,1-difluoroethanesulfonic acid, 1,1-difluoro-n-propanesulfonic acid, 1,1-difluoro-n-butanesulfonic acid, 1,1-difluoro-n- Octane sulfonic acid, 1-trifluoromethyl-n-propane sulfonic acid, 1-trifluoromethyl-n-butane sulfonic acid,
1-trifluoromethyl-n-octane sulfonic acid,
1,1-bis (trifluoromethyl) ethanesulfonic acid, 1,1-bis (trifluoromethyl) -n-propanesulfonic acid, 1,1-bis (trifluoromethyl)-
n-butane sulfonic acid, 1,1-bis (trifluoromethyl) -n-octane sulfonic acid,

In the bonds of the groups represented by the general formulas (α-1) to (α-7), --CF ₂ SO ₃ H, --CHFSO ₃ H,
-CH (CF ₃₎ SO ₃ H or _{-C (CF 3) 2 SO 3} H
An acid to which a group of is bonded, for example, the following formulas (II-1) to (II-40)
Acid, etc. can be mentioned.

[0060]

[Chemical 27]

[0061]

[Chemical 28]

[0062]

[Chemical 29]

[0063]

[Chemical 30]

[0064]

[Chemical 31]

[0065]

[Chemical 32]

[0066]

[Chemical 33]

[0067]

[Chemical 34]

[0068]

[Chemical 35]

[0069]

[Chemical 36]

[0070]

[Chemical 37]

[0071]

[Chemical 38]

[0072]

[Chemical Formula 39]

[0073]

[Chemical 40]

[0074]

[Chemical 41]

[0075]

[Chemical 42]

[0076]

[Chemical 43]

[0077]

[Chemical 44]

[0078]

[Chemical formula 45]

[0079]

[Chemical formula 46]

Examples of preferable acid (III) include methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, n-butanesulfonic acid, i-butanesulfonic acid, sec-butanesulfonic acid and t-butane. Linear, branched or cyclic alkyl sulfonic acids such as sulfonic acid, n-pentane sulfonic acid, n-hexane sulfonic acid, n-octane sulfonic acid, cyclopentane sulfonic acid, cyclohexane sulfonic acid; benzene sulfonic acid, p- Toluenesulfonic acid, benzylsulfonic acid, α
-Aromatic sulfonic acids such as naphthalene sulfonic acid and β-naphthalene sulfonic acid; 10-camphor sulfonic acid and -SO on the bond of the group represented by the general formulas (α-1) to (α-7). _The acid etc. which the ₃ H group couple | bonded can be mentioned.

Further, as preferable acid (IV), for example, acetic acid, n-propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, benzoic acid, salicylic acid,
Phthalic acid, terephthalic acid, α-naphthalenecarboxylic acid,
β-naphthalenecarboxylic acid, cyclobutanecarboxylic acid,
Cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3
-Cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-norbornanecarboxylic acid, 2,3-norbornanedicarboxylic acid Acid, norbornyl-2-acetic acid, 1-adamantanecarboxylic acid, 1-adamantaneacetic acid, 1,3-adamantanedicarboxylic acid, 1,
3-adamantanediacetic acid, lithocholic acid, deoxycholic acid, chenodeoxycholic acid, cholic acid and the bonds of the groups represented by the general formulas (α-1) to (α-7) have -CO
The acid etc. which the OH group couple | bonded can be mentioned.

Acid generator (B1) and acid generator (B2)
Examples thereof include onium salt compounds, sulfone compounds, sulfonic acid compounds, carboxylic acid compounds, diazoketone compounds, halogen-containing compounds and the like. It Acid (I), Acid (II), Acid (III) or Acid (I
Examples of the onium salt compound generating V) include diphenyliodonium salt, bis (4-t-butylphenyl) iodonium salt, triphenylsulfonium salt, 4
-Hydroxyphenyl phenyl methylsulfonium salt, cyclohexyl 2-oxocyclohexyl methylsulfonium salt, dicyclohexyl 2-oxocyclohexylsulfonium salt, 2-oxocyclohexyldimethylsulfonium salt, 4-hydroxyphenyl benzyl methylsulfonium salt, 1 -Naphthyldimethylsulfonium salt, 1-naphthyldiethylsulfonium salt, 1- (4-cyanonaphthyl) dimethylsulfonium salt, 1- (4-cyanonaphthyl) diethylsulfonium salt, 1- (4-nitronaphthyl) dimethylsulfonium salt, 1 -(4-Nitronaphthyl) diethylsulfonium salt, 1- (4-methylnaphthyl) dimethylsulfonium salt, 1- (4-methylnaphthyl) diethylsulfonium salt, 1- (4-hydride Kishinafuchiru) dimethyl sulfonium salts, 1- (4-hydroxy-naphthyl) diethyl sulfonium salt,

1- [1- (4-hydroxynaphthyl)]
Tetrahydrothiophenium salt, 1- [1- (4-ethoxynaphthyl)] tetrahydrothiophenium salt, 1-
[1- (4-n-Butoxynaphthyl)] tetrahydrothiophenium salt, 1- [1- (4-methoxymethoxynaphthyl)] tetrahydrothiophenium salt, 1- [1-
(4-Ethoxytomethoxynaphthyl)] tetrahydrothiophenium salt, 1- [1- {4- (1-methoxyethoxy) naphthyl}] tetrahydrothiophenium salt, 1-
[1- {4- (2-Methoxyethoxy) naphthyl}] tetrahydrothiophenium salt, 1- [1- (4-methoxycarbonyloxynaphthyl)] tetrahydrothiophenium salt, 1- [1- (4-ethoxy) Carbonyloxynaphthyl)] tetrahydrothiophenium salt, 1- [1
-(4-n-propoxycarbonyloxynaphthyl)]
Tetrahydrothiophenium salt, 1- [1- (4-i-
Propoxycarbonyloxynaphthyl)] tetrahydrothiophenium salt, 1- [1- (4-n-butoxycarbonyloxynaphthyl)] tetrahydrothiophenium salt, 1- [1- (4-t-butoxycarbonyloxynaphthyl)] Tetrahydrothiophenium salt, 1- [1-
{4- (2-Tetrahydrofuranyloxy) naphthyl}] tetrahydrothiophenium salt, 1- [1- {4
-(2-tetrahydropyranyloxy) naphthyl}] tetrahydrothiophenium salt, 1- [1- (4-benzyloxynaphthyl)] tetrahydrothiophenium salt,
Examples thereof include 1- [1- (1-naphthylacetomethyl)] tetrahydrothiophenium salt.

Acid (I), acid (II) or acid (II
Examples of the sulfone compound generating I) include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds. Also,
Examples of the sulfonic acid compound that generates the acid (I), the acid (II) or the acid (III) include sulfonic acid ester, sulfonic acid imide, aryl sulfonic acid ester, and imino sulfonate. Also acid (IV)
Examples of the carboxylic acid compound that generates carboxylic acid include carboxylic acid ester, carboxylic acid imide, and carboxylic acid cyanate.

As the diazoketone compound which generates an acid (I), an acid (II), an acid (III) or an acid (IV),
For example, 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds and the like can be mentioned. Furthermore, acid (I), acid (II), acid (II
Examples of the halogen-containing compound that generates I) or the acid (IV) include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound.

In the present invention, the amount of the acid generator (B) used is usually 1 to 20 relative to 100 parts by weight of the resin (A).
Parts by weight, preferably 2 to 10 parts by weight. in this case,
When the amount of the acid generator (B) used is less than 1 part by weight, the sensitivity and resolution when used as a resist tend to decrease, while when it exceeds 20 parts by weight, the radiation transmittance of the resist film when used as a resist is increased. May decrease and the pattern shape may be impaired. The amount of acid generator (B2) used is
It is usually 5 parts by weight or less, preferably 3 parts by weight or less, relative to 100 parts by weight of the resin (A).

Dissolution Control Agent In a preferred embodiment of the radiation-sensitive resin composition of the present invention, a compound represented by the following general formula (3) (hereinafter referred to as “compound (3)”) is further used as a dissolution control agent. And a compound represented by the following general formula (4) (hereinafter referred to as “compound (4)”) (hereinafter referred to as “dissolution control agent (C1)”), And / or a polyketone having a repeating unit represented by the following general formula (5) and the following general formula (6)
It is possible to contain at least one kind selected from the group of polyspiroketals having a repeating unit represented by (hereinafter referred to as “dissolution control agent (C2)”). The radiation-sensitive resin composition of the present invention contains the dissolution control agent (C1) and / or the dissolution control agent (C2), whereby the dissolution contrast and the dissolution rate when used as a resist can be controlled more appropriately. it can.

[0088]

[Chemical 47]

[In the general formula (3) and the general formula (4), each X independently of one another is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. 10 linear or branched fluorinated alkyl groups or groups represented by the following general formula (i) (hereinafter referred to as "functional group (i)").

[0090]

[Chemical 48]

(In the formula, Y represents a single bond, a methylene group, a cyclohexylene group or a phenylene group, Z represents a hydrogen atom or a monovalent organic group which dissociates with an acid to generate a hydrogen atom, and r represents 0 or 1) and at least one of X is a functional group (i), and p and q are each an integer of 0 to 2. ]

[0092]

[Chemical 49] [In the general formulas (5) and (6), each R ³ is independently of each other a hydrogen atom, a fluorine atom, a hydroxyl group, a methyl group, an ethyl group, a trifluoromethyl group, a pentafluoroethyl group, and t-butoxycarbonyl. Group, t-butoxycarbonylmethyl group or the following general formula (ii)

[0093]

[Chemical 50] (In the formula, R ⁴ is a hydrogen atom, a t-butoxycarbonyl group,
A methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group or a 1-ethoxyethyl group, Rf ₁ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and z
Is an integer of 0 to 3. ) Represents a group represented by. ]

In the general formulas (3) and (4), examples of the linear or branched alkyl group having 1 to 10 carbon atoms of X include, for example, methyl group, ethyl group, n-propyl group, i. -Propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -A decyl group etc. can be mentioned.

Examples of the linear or branched fluorinated alkyl group having 1 to 10 carbon atoms for X include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group and heptafluoro- group. n-
Propyl group, heptafluoro-i-propyl group, nonafluoro-n-butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, perfluoro-n
-Heptyl group, perfluoro-n-octyl group, perfluoro-n-nonyl group, perfluoro-n-decyl group and the like can be mentioned.

In the functional group (i) representing X, the two bonds in the cyclohexylene group and the phenylene group of Y are respectively in the 1,2-position, 1,3-position or 1,4-position. You can

Examples of the monovalent organic group which dissociates with a Z acid to generate a hydrogen atom include, for example, t-butoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group and 9-fluorene group. Nylmethylcarbonyl group, 2,2,2-trichloroethylcarbonyl group, 2- (trimethylsilyl) ethylcarbonyl group, i-butylcarbonyl group, vinylcarbonyl group, allylcarbonyl group, benzylcarbonyl group, 4-ethoxy-1-naphthyl Organic carbonyl groups such as carbonyl group and methyldithiocarbonyl group;

Methoxymethyl group, methylthiomethyl group,
Ethoxymethyl group, ethylthiomethyl group, t-butoxymethyl group, t-butylthiomethyl group, (phenyldimethylsilyl) methoxymethyl group, benzyloxymethyl group,
t-butoxymethyl group, siloxymethyl group, 2-methoxyethoxymethyl group, 2,2,2-trichloroethoxymethyl group, bis (2-chloroethoxy) methyl group, 2-
(Trimethylsilyl) ethoxymethyl group, 1-methoxycyclohexyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 1-methoxyethyl group, 1- Ethoxyethyl group, 1- (2-chloroethoxy) ethyl group, 1-methyl-1-methoxyethyl group, 1-methyl-1-benzyloxyethyl group, 1- (2-chloroethoxy) ethyl group, 1
-Methyl-1-benzyloxy-2-fluoroethyl group,
2,2,2-trichloroethyl group, 2-trimethylsilylethyl group, 2- (phenylselenyl) ethyl group,
An organic group which forms an acetal structure by combining with an oxygen atom in the general formula (i);

Trimethylsilyl group, triethylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, dimethylethylsilyl group, t-butyldimethylsilyl group, t
-Butyldiphenylsilyl group, tribenzylsilyl group,
Tri-p-xylylsilyl group, triphenylsilyl group,
Alkylsilyl groups such as diphenylmethylsilyl group and t-butylmethoxyphenylsilyl group; 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 2-
Examples of the alkyl-substituted alicyclic group such as methyl-2-norbornyl group, 2-ethyl-2-norbornyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group and 1-ethylcyclohexyl group. be able to.

Among the monovalent organic groups which are dissociated by these acids to generate hydrogen atoms, t-butoxycarbonyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group and the like are preferable. .

Preferred compounds (3) are, for example,
Examples thereof include compounds represented by the following general formula (3-1) to formula (3-4).

[0102]

[Chemical 51]

[0103]

[Chemical 52]

[In the general formulas (3-1) to (3-4), each R ⁸ is independently a hydrogen atom, a t-butoxycarbonyl group, a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group or 1-ethoxyethyl group, each Rf ₂
Are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group. However, in the general formula (3-3) and the general formula (3-4), eight Rf _{2 s} do not simultaneously take hydrogen atoms. ]

Examples of preferable compound (4) include compounds represented by the following general formulas (4-1) to (4-5).

[0106]

[Chemical 53]

[0107]

[Chemical 54]

[0108]

[Chemical 55]

[In the general formulas (4-1) to (4-5), each R ⁸ is independently a hydrogen atom, a t-butoxycarbonyl group, a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group or 1-ethoxyethyl group, each Rf ₂
Are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group. However, in the general formula (4-3) and the general formula (4-4), four Rf ₂ 's do not simultaneously take hydrogen atoms. ]

In the dissolution control agent (C1), the compound (3) is, for example, the following formula (3-1-1) or formula (3-1)
-2), a compound of formula (3-2-1) or formula (3-2-2) is more preferable, and examples of the compound (4) include the following formula (4-1-1) and formula (4 -1-2), formula (4-2-1), formula (4-2
-2) or the compound of formula (4-5-1) is more preferable.

[0111]

[Chemical 56]

[0112]

[Chemical 57]

[0113]

[Chemical 58]

[0114]

[Chemical 59]

[0115]

[Chemical 60]

As the dissolution control agent (C2), polyspiroketal having a repeating unit represented by the following formula (6-1) is more preferable.

[0117]

[Chemical formula 61]

The Mw of the polyketone and the polyspiroketal is usually 300 to 100,000, preferably 800 to 3,000.

In the present invention, the amount of the dissolution control agent used is
It is usually 50 parts by weight or less, preferably 30 parts by weight or less, relative to 100 parts by weight of the resin (A). In this case, if the amount of the dissolution control agent used exceeds 50 parts by weight, the heat resistance of the resist tends to decrease.

Other Additives Various additives such as an acid diffusion controller, a surfactant and a sensitizer may be added to the radiation-sensitive resin composition of the present invention, if necessary. The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change due to exposure or heat treatment during the resist pattern forming step. As such a nitrogen-containing organic compound, for example, the following general formula (9)

[0121]

[Chemical formula 62] [In the general formula (9), each R ⁹ independently represents 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. Indicates a group. ]

A compound represented by the following (hereinafter referred to as "nitrogen-containing compound (a)"), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as "nitrogen-containing compound (b)"),
Examples thereof include polyamino compounds and polymers having three or more nitrogen atoms (hereinafter collectively referred to as “nitrogen-containing compound (c)”), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like. .

As the nitrogen-containing compound (a), 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
-Di (cyclo) alkylamines such as octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-
Butylamine, tri-n-pentylamine, tri-n-
Hexylamine, tri-n-heptylamine, tri-n
-Octylamine, tri-n-nonylamine, tri-n
-Tri (cyclo) alkylamines such as decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine; aniline, N-
Aromatic amines such as methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine and naphthylamine can be mentioned.

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. it can. Examples of the nitrogen-containing compound (c) include polyethyleneimine, polyallylamine, and N- (2-dimethylaminoethyl) acrylamide polymers.

Examples of the amide group-containing compound include N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N, N'N'-tetra-t-butoxycarbonylhexamethylenediamine, N, N. '-The-
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, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, formamide , N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide,
Examples thereof include N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone and N-methylpyrrolidone.

Examples of the urea compound include urea, methylurea, 1,1-dimethylurea and 1,3-
Examples thereof include dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea and tri-n-butylthiourea. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole and 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-
Methyl pyridine, 2-ethyl pyridine, 4-ethyl pyridine, 2-phenyl pyridine, 4-phenyl pyridine,
Pyridines such as 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline and acridine; piperazine, piperazine such as 1- (2-hydroxyethyl) piperazine Besides, pyrazine, pyrazole,
Pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, etc. Can be mentioned. These acid diffusion control agents can be used alone or in admixture of two or more.

In the present invention, the amount of the acid diffusion controller used is usually 15 parts by weight or less, preferably 10 parts by weight or less, relative to 100 parts by weight of the resin (A). in this case,
If the amount of the acid diffusion controller used exceeds 15 parts by weight, the sensitivity as a resist and the developability of the exposed area tend to be lowered. If the amount of the acid diffusion control agent used is less than 0.01 parts by weight, the pattern shape and dimensional fidelity of the resist may decrease depending on the process conditions.

The surface active agent is a component having an effect of improving coating property, striation, developability and the like. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl 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. These surfactants may be used alone or in admixture of two or more. In the present invention,
The amount of the surfactant used is usually 2 parts by weight or less with respect to 100 parts by weight of the resin (A).

The sensitizer has a function of absorbing the energy of radiation and transmitting the energy to the acid generator (B), thereby increasing the amount of acid produced. It has the effect of improving the apparent sensitivity of the resin composition. Examples of such sensitizers include acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrenes, anthracenes, and phenothiazines. These sensitizers can be used alone or in admixture of two or more. In the present invention, the amount of the sensitizer used is
It is usually 50 parts by weight or less with respect to 100 parts by weight of the resin (A). In addition, 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.
The adhesion with the substrate can be improved. Further, as additives other than the above, an antihalation agent, a storage stabilizer, an antifoaming agent and the like can be mentioned.

Preparation of Composition Solution The radiation-sensitive resin composition of the present invention usually has a total solid content concentration of usually 1 to 20% by weight, preferably 5 to 15% by weight when used. After being dissolved in a solvent, it is prepared as a composition solution by filtering with a filter having a pore size of about 0.2 μm. Examples of the solvent used for preparing the composition solution include 2-
Butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3
-Linear or branched ketones such as -methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone; cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2 -Methylcyclohexanone, 2,6-dimethylcyclohexanone,
Cyclic ketones such as isophorone; propylene glycol monomethyl ether acetate, 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-
Propylene glycol monoalkyl ether acetates such as butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate,
N-Propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, 2
-Alkyl 2-hydroxypropionates such as t-butyl hydroxypropionate; 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate In addition to acid alkyls,

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, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutyrate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, ethyl acetate, N-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzylethyl ether, di -N-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid,
Examples thereof include 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate and propylene carbonate.

These solvents may be used alone or in admixture of two or more, but among them, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates , 2-hydroxypropionate alkyls, 3-alkoxypropionate alkyls, γ-butyrolactone and the like are preferable.

Method of forming resist pattern The radiation-sensitive resin composition of the present invention can be used very suitably as a chemically amplified resist. In the chemically amplified resist, the acid dissociable protective group in the resin (A) is dissociated by the action of the acid generated from the acid generator (B) upon exposure, and the exposed portion of the resist is dissolved in the alkali developing solution. And the exposed portion is dissolved and removed by an alkali developing solution to obtain a positive resist pattern. When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution is coated with a suitable coating means such as spin coating, cast coating, roll coating, for example, with a silicon wafer or aluminum. A resist film is formed by applying it on a substrate such as
It is called "PB". Then, the resist film is exposed so as to form a predetermined resist pattern. As the radiation used at that time, visible light, ultraviolet rays, far ultraviolet rays, depending on the type of the acid generator (B) used,
An electron beam, an X-ray or the like is appropriately selected and used.
Far ultraviolet rays having a wavelength of 3 nm or less are preferable, and F ₂ excimer laser (wavelength 157 nm), Kr ₂ excimer laser (wavelength 147 nm) or ArKr excimer laser (wavelength 134 nm) is particularly preferable. In the present invention, it is preferable to perform a heat treatment (hereinafter referred to as “PEB”) after the exposure, whereby the dissociation reaction of the acid dissociable protective group proceeds smoothly. The PEB heating conditions vary depending on the composition of the radiation-sensitive resin composition, but are usually 30 to 2
The temperature is 00 ° C, preferably 50 to 170 ° C.

In 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 Unexamined Patent Publication No. 12452, an organic or inorganic antireflection film can be formed on a substrate to be used, and the influence of basic impurities contained in an environmental atmosphere can be prevented. To prevent this, for example, JP-A-5-18
As disclosed in Japanese Patent No. 8598, a protective film may be provided on the resist film, or these techniques may be used in combination. Then, by developing the exposed resist film with an alkaline developer,
A predetermined resist pattern is formed. Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, and the like. Methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline,
1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-
An alkaline aqueous solution in which at least one alkaline compound such as nonene is dissolved is preferable. The concentration of the alkaline aqueous solution is usually 10% 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.

Further, for example, an organic solvent can be added to the alkaline aqueous solution. Examples of the organic solvent include acetone, methyl ethyl ketone, and methyl i.
-Ketones such as butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t- Butyl alcohol, cyclopentanol, cyclohexanol, 1,
Alcohols such as 4-hexanediol and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; ethyl acetate, n-butyl acetate, i-acetic acid
Examples thereof include esters such as amyl; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone, dimethylformamide, and the like. These organic solvents may be used alone or in admixture of two or more. The amount of the organic solvent used is preferably 100% by volume or less with respect to the alkaline aqueous solution. 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, an appropriate amount of a surfactant or the like can be added to the alkaline aqueous solution. After developing with an alkaline developer, it is generally washed with water and dried.

[0136]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described more specifically below with reference to examples. However, the present invention is not limited to these examples. Here, parts are by weight unless otherwise specified.

Synthesis Example 1 An autoclave equipped with a stirrer was charged with 30 g of a monomer represented by the following formula (7-2) and 90 mg of diisopropyl peroxydicarbonate as a polymerization initiator, and deaeration and nitrogen introduction were repeated under stirring, Finally, after degassing, polymerization was carried out at 40 ° C. for 24 hours. After completion of polymerization
After cooling the reaction solution to room temperature and reducing the pressure in the autoclave to atmospheric pressure, the reaction product was poured into ethanol, the coagulated resin was separated, further washed with ethanol, and dried to obtain Mw of 11 1,000 resin (A) 16.
2 g was obtained. This resin (A) is referred to as resin (A-1).

[0138]

[Chemical formula 63]

Synthesis Example 2 In an autoclave equipped with a stirrer, 27.1 g of the monomer of the formula (7-1), 3.5 g of the monomer of the formula (7-2) and diisopropyl peroxydicarbonate as a polymerization initiator. Charge 90 mg, repeat the degassing process and the nitrogen introducing process under stirring, and finally perform the degassing process, and then 40 ° C.
Polymerization was carried out for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the pressure in the autoclave was reduced to normal pressure, the reaction product was poured into ethanol, the coagulated resin was separated, further washed with ethanol, and dried. , M
21.9 g of resin (A) having w of 11,700 was obtained. This resin (A) is referred to as resin (A-2).

Synthesis Example 3 In an autoclave equipped with a stirrer, 24.1 g of the monomer of the formula (7-1), 7.0 g of the monomer of the formula (7-2) and diisopropyl peroxydicarbonate as a polymerization initiator were used. Charge 90 mg, repeat the degassing process and the nitrogen introducing process under stirring, and finally perform the degassing process, and then 40 ° C.
Polymerization was carried out for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the pressure in the autoclave was reduced to normal pressure, the reaction product was poured into ethanol, the coagulated resin was separated, further washed with ethanol, and dried. , M
23.2 g of resin (A) having w of 12,100 was obtained. This resin (A) is referred to as resin (A-3).

Synthesis Example 4 20.0 g of the monomer of the formula (7-1), 10.0 g of the monomer of the formula (7-2) and diisopropyl peroxydicarbonate as a polymerization initiator were placed in an autoclave equipped with a stirrer. 90 mg was charged, the degassing treatment and the nitrogen introducing treatment were repeated under stirring, and finally the degassing treatment was performed.
Polymerization was performed at 24 ° C. for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the pressure in the autoclave was reduced to normal pressure, the reaction product was poured into ethanol, the coagulated resin was separated, further washed with ethanol, and dried. ,
23.2 g of resin (A) having Mw of 12,700 was obtained. This resin (A) is referred to as resin (A-4).

Synthesis Example 5 In an autoclave equipped with a stirrer, 18.1 g of the monomer of the formula (7-1), 14.0 g of the monomer of the formula (7-2) and diisopropyl peroxydicarbonate as a polymerization initiator were added. 90 mg was charged, the degassing treatment and the nitrogen introducing treatment were repeated under stirring, and finally the degassing treatment was performed.
Polymerization was performed at 24 ° C. for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the pressure in the autoclave was reduced to normal pressure, the reaction product was poured into ethanol, the coagulated resin was separated, further washed with ethanol, and dried. ,
21.1 g of resin (A) having an Mw of 12,600 was obtained. This resin (A) is referred to as resin (A-5).

The Mw of each resin (A) is G manufactured by Tosoh Corporation.
PC column (2 G2000HXL, 1 G3000HXL 1
, G4000HXL 1), flow rate 1.0 ml / min, elution solvent tetrahydrofuran, column temperature 4
It was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis condition of 0 ° C.

Evaluation Example 1 (Radiation Transmittance and Absorbance at 157 nm Wavelength) A solution prepared by dissolving the resin (A) obtained in each synthesis example in 2-heptanone was applied onto a magnesium fluoride substrate by spin coating, and 110 ° C. Film thickness of 1,0
The transmittance and the absorbance of the 00Å film at wavelengths of 130 to 200 nm were measured. As a result, it was confirmed that all the resins (A) had extremely high transmittance. Among the measurement results, Table 1 shows the transmittance and the absorbance at a wavelength of 157 nm.

[0145]

[Table 1]

[0146]

EXAMPLES Evaluation Example 2 (Examples 1 to 23; resolution by ArF excimer laser exposure) Resin 2 (A), acid generator (B), dissolution controller (C) and acid diffusion controller 2 shown in Table 2 were used. -A solution prepared by dissolving heptanone in a commercially available antireflection film DUV-30J (film thickness 520
Å) was applied on the silicone wafer by spin coating, and on a hot plate kept at 110 ° C,
PB was performed for 90 seconds to form a resist film having a film thickness of 100 nm. Then, for each resist coating, ArF
An excimer laser exposure device (lens numerical aperture 0.55, exposure wavelength 193 nm) was used to change the exposure amount and perform exposure 1
PEB for 90 seconds on a hot plate kept at 10 ° C
After that, a positive type resist pattern was formed by developing with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, washing with water, and drying. At this time, line and line with a line width of 160 nm
The exposure amount for forming the space pattern (1L1S) with a line width of 1: 1 was taken as the optimum exposure amount, and the minimum resist pattern size (ArF resolution) resolved by this optimum exposure amount was evaluated. The evaluation results are shown in Table 2.

Evaluation Example 3 (Examples 1 to 23; Resolution by F ₂ Excimer Laser Exposure) The resin (A), the acid generator (B), the dissolution control agent and the acid diffusion control agent shown in Table 2 were converted to 2-heptanone. The dissolved solution
A commercially available anti-reflection film DUV-30J (film thickness 520Å) was applied on a silicone wafer by spin coating, and PB was performed for 90 seconds on a hot plate kept at 110 ° C to form a resist film having a film thickness of 120 nm. Formed. Then, an F ₂ excimer laser exposure apparatus (lens numerical aperture =
0.60, in Examples 19 to 23, lens numerical aperture = 0.8
5, the exposure wavelength was changed to 157 nm) to perform exposure, and PEB was performed for 90 seconds on a hot plate kept at 110 ° C., and then at 23 ° C. with a 2.38 wt% tetramethylammonium hydroxide aqueous solution. Developed for 20 seconds, washed with water, and dried to form a positive resist pattern. At this time, the exposure amount for forming a line-and-space pattern (1L1S) having a line width of 130 nm with a line width of 1: 1 is set as the optimum exposure amount, and the minimum resist pattern size ( (F2 resolution)
Was evaluated. The evaluation results are shown in Table 2.

In Table 2, the components other than the resin (A) are as follows. Acid generator (B) B-1: triphenylsulfonium trifluoromethanesulfonate B-2: triphenylsulfonium nonafluoro-n-butanesulfonate B-3: compound of the following formula (B-3)

[0149]

[Chemical 64]

B-4: Compound of the following formula (B-4)

[0151]

[Chemical 65]

B-5: Triphenylsulfonium 10-camphorsulfonate

Dissolution controlling agent C-1: Compound of the formula (3-1-1) C-2: Compound of the formula (6-1) (Mw = 1,500)

Acid diffusion control agent D-1: 2-phenylbenzimidazole D-2: tri-n-butylamine

[0155]

[Table 2]

[0156]

Industrial Applicability The radiation-sensitive resin composition of the present invention has high transparency at a wavelength of 193 nm or less, particularly 157 nm or less, and a chemically amplified resist having a high resolution without deteriorating sensitivity, pattern shape, developability and the like. As a result, it can be very suitably used for manufacturing integrated circuit elements, which are expected to be further miniaturized in the future.

Continued front page    (72) Inventor Akihiro Hayashi             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. (72) Inventor Tsutomu Shimokawa             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F-term (reference) 2H025 AB16 AC04 AC05 AC06 AC08                       AD03 BE00 BG00 FA03 FA12                       FA17                 4J100 AS13P AS13Q BA02P BA02Q                       BA03P BA05P BA05Q BB07P                       BB07Q CA01 CA04 CA21                       JA38

Claims (5)

[Claims] 1. (A) A resin protected by an alkali-insoluble or alkali-insoluble acid dissociable protective group having a repeating unit represented by the following general formula (1), which is soluble in alkali by the action of an acid. And a radiation-sensitive resin composition containing (B) a radiation-sensitive acid generator that generates trifluoromethanesulfonic acid or an acid represented by the following general formula (I) upon irradiation with radiation. object. [Chemical 1] [In the general formula (1), each R ¹ is independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkyl group having 1 to 10 carbon atoms. Of the fluorinated alkyl group, each A independently represents -O- or a group represented by the following formula (2), and at least two A are groups represented by the formula (2):
m and n are 0 or 1, respectively, and (m + n) = 1. [Chemical 2] (In the formula, each R ² is independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched fluorine atom having 1 to 10 carbon atoms. Alkyl group or a monovalent group which is dissociated with an acid to form a hydroxyl group.)] [In the general formula (I), Ra is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 20 carbon atoms, A cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms or a cyclic monovalent fluorinated hydrocarbon group having 3 to 20 carbon atoms is shown, and the monovalent hydrocarbon group and the monovalent fluorinated carbon group are shown. The hydrogen group may be substituted, and each Rb independently represents a fluorine atom or a trifluoromethyl group. ] 2. The radiation-sensitive resin according to claim 1, wherein the repeating unit represented by the general formula (1) in the component (A) coexists with a unit having n = 0 and a unit having n = 1. Composition. 3. The component according to claim 1, wherein the repeating unit represented by the general formula (1) in the component (A) is a unit in which all three A's are groups represented by the formula (2). The radiation-sensitive resin composition of. 4. The method according to claim 1, further comprising (C1) at least one selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (4). The radiation-sensitive resin composition according to any one of 3 above. [Chemical 4] [In the general formulas (3) and (4), each X independently of one another is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a straight chain having 1 to 10 carbon atoms. A chain or branched fluorinated alkyl group, or a group represented by the following general formula (i): (In the formula, Y represents a single bond, a methylene group, a cyclohexylene group or a phenylene group, Z represents a hydrogen atom or a monovalent organic group which dissociates with an acid to generate a hydrogen atom, and r is 0 or 1. .) And at least one of X is a group represented by the general formula (i), and p and q are each an integer of 0 to 2. ] 5. At least one selected from the group consisting of (C2) a polyketone having a repeating unit represented by the following general formula (5) and a polyspiroketal having a repeating unit represented by the following general formula (6). The radiation-sensitive resin composition according to claim 1, further comprising a seed. [Chemical 6] [In the general formulas (5) and (6), each R ³ is independently of each other a hydrogen atom, a fluorine atom, a hydroxyl group, a methyl group, an ethyl group, a trifluoromethyl group, a pentafluoroethyl group, and t-butoxycarbonyl. Group, t-butoxycarbonylmethyl group or the following general formula (ii): (In the formula, R ⁴ is a hydrogen atom, a t-butoxycarbonyl group,
A methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group or a 1-ethoxyethyl group, Rf ₁ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and z
Is an integer of 0 to 3. ) Represents a group represented by. ]