JP2003241383A - Radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition excellent in contrast, capable of forming a fine resist pattern with a high degree of accuracy and excellent also in transparency to a radiation, sensitivity and resolution. <P>SOLUTION: The radiation-sensitive resin composition comprises (A) a resin comprising an acid-dissociable group-containing norbornene compound typified by 5-[(1-methylcyclohexyl)oxycarbonyl]norbornene or 5-(2-methyl-1- adamantyloxycarbonyl)norbornene and maleic anhydride, (B) a radiation-sensitive acid generator and (C) a compound typified by a di-t-butyl 1,3- adamantanedicarboxylate or 2,5-dimethyl-2,5-di(1-adamantylcarbonyloxy)hexane. Preferably the resin (A) further comprises a polar group-containing alicyclic ester of (meth)acrylic acid typified by 3-hydroxy-1-adamantyl (meth)acrylate. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a radiation-sensitive resin composition, and more specifically, it is far ultraviolet ray such as KrF excimer laser, ArF excimer laser or F ₂ excimer laser, X-ray such as synchrotron radiation, and electron. The present invention relates to a radiation-sensitive resin composition that can be suitably used as a chemically amplified resist useful for microfabrication using various kinds of radiation such as charged particles such as rays.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit devices, a lithography process capable of microfabrication at a level of 0.20 .mu.m or less is recently required in order to obtain a higher degree of integration. Has been done. But,
In the conventional lithography process, near-ultraviolet rays such as i-rays are generally used as radiation, and it is said that with this near-ultraviolet rays, fine processing at the subquarter micron level is extremely difficult. 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-wavelength radiation include bright line spectra of mercury lamps, deep ultraviolet rays represented by excimer lasers, X-rays, electron beams, and the like.
The rF excimer laser (wavelength 248 nm), the ArF excimer laser (wavelength 193 nm) or the F ₂ excimer laser (wavelength 157 nm) is drawing attention. As a resist suitable for irradiation by such an excimer laser, a component having an acid-dissociable functional group and a component that generates an acid by irradiation with radiation (hereinafter, referred to as “exposure”) (hereinafter, “radiation-sensitive acid generator”). A lot of resists (hereinafter, referred to as "chemically amplified resists") that utilize the chemical amplification effect of () are proposed. As the chemically amplified resist, for example, Japanese Patent Publication No. 27660/1990 contains a polymer having a t-butyl ester group of a carboxylic acid or a t-butyl carbonate group of a phenol and a radiation-sensitive acid generator. A resist that does is proposed. In this resist, the t-butyl ester group or t-butyl carbonate group present in the polymer is dissociated by the action of the acid generated by exposure, and the polymer is an acidic functional group consisting of a carboxyl group or a phenolic hydroxyl group. This is due to the fact that it has a group, and as a result, the exposed region of the resist film becomes easily soluble in an alkali developing solution.

By the way, most of the conventional chemically amplified resists are based on a phenolic resin.
In the case of such a resin, if far ultraviolet rays are used as radiation, the far ultraviolet rays are absorbed due to the aromatic ring in the resin, so that the exposed far ultraviolet rays cannot sufficiently reach the lower layer portion of the resist coating. There is a defect that the amount of exposure is large in the upper layer part of the resist coating and small in the lower layer part, and the resist pattern after development becomes a trapezoid that becomes thinner at the upper part and becomes thicker toward the lower part, and sufficient resolution cannot be obtained. There was such a problem. In addition, when the resist pattern after development has a trapezoidal shape, the desired dimensional accuracy cannot be achieved in the next step, that is, during etching or ion implantation, which is a problem. In addition, 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 will be high, which makes it difficult to control the 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 typified by polymethylmethacrylate is a highly preferable resin from the viewpoint of radiation transmittance because it has high transparency to deep ultraviolet rays, and is disclosed in, for example, JP-A-4-226461. Proposes a chemically amplified resist using a methacrylate resin. However, although this composition is excellent in terms of fine processing performance, it does not have an aromatic ring and thus has a drawback of low dry etching resistance. In this case as well, it is difficult to perform highly accurate etching processing. Therefore, it cannot be said that it has both transparency to radiation and resistance to dry etching.

Further, as one of measures for improving dry etching resistance of a chemically amplified resist without impairing transparency to radiation, an aliphatic ring is introduced into a resin component in the resist instead of an aromatic ring. A method of doing so is known, and for example, JP-A-7-234511 proposes a chemically amplified resist using a (meth) acrylate resin having an aliphatic ring. However,
In this resist, as the acid dissociable functional group of the resin component, a group that is relatively easily dissociated by a conventional acid (for example, an acetal-based functional group such as a tetrahydropyranyl group) or a group that is relatively difficult to dissociate by an acid (for example, , T-butyl ester group, t-butyl carbonate group, etc.) are used, and in the case of the former resin component having an acid-dissociable functional group, basic physical properties of the resist, particularly sensitivity and pattern. Although the shape is good, there is a problem in storage stability as a composition, and in the latter resin component having an acid-dissociable functional group, on the contrary, storage stability is good, but the basic physical properties of the resist, particularly There is a drawback that sensitivity and pattern shape are impaired. Furthermore, since an aliphatic ring is introduced into the resin component in this resist, the hydrophobicity of the resin itself becomes very high, and there is a problem in terms of adhesiveness to the substrate.

Further, as one of the measures for improving the properties of the chemically amplified radiation-sensitive composition as a resist, a large number of multi-component compositions of three or more components containing a high-molecular or low-molecular additive are proposed. For example, Japanese Patent Laid-Open No. 7-2
No. 34511 discloses a resin having a hydrophilic group,
Copolymer of p-hydroxystyrene and tetrahydropyranyl (meth) acrylate or t-butyl (meth) acrylate, p-hydroxystyrene and p-tetrahydropyranyloxycarbonyloxystyrene or p-t-butoxycarbonyloxy By adding t-butyl 3-adamantanecarboxylate as a hydrophobic compound to a resist containing a p-hydroxystyrene copolymer such as a copolymer with styrene, a delay from exposure to heat treatment after exposure can be achieved. It is disclosed that the effect of time is lessened, or stable patterning is possible even in the case of a resist containing a highly hydrophobic group. However,
In the conventional multi-component chemically amplified radiation-sensitive compositions including those disclosed in JP-A-7-234511, contrast,
It is still unsatisfactory from the viewpoint of total performance as a resist including transparency to radiation, sensitivity and resolution.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In particular, the object of the present invention is to provide excellent contrast, capable of forming a fine resist pattern with high accuracy, and transparency, sensitivity to radiation,
It is intended to provide a radiation-sensitive resin composition useful as a chemically amplified resist excellent in resolution and the like.

[0007]

According to the present invention, the above-mentioned problems are (A) a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (1-2). And an alkali-insoluble or sparingly-soluble resin that is alkali-soluble by the action of an acid, (B) a radiation-sensitive acid generator, and (C) the following general formula (2-1) or general formula (2- 2) A radiation-sensitive resin composition containing a compound having a molecular weight of 1,000 or less

[0008]

[Chemical 4]

[In the general formula (1-1), each R ¹ is independently a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a straight chain having 1 to 4 carbon atoms. or shows a branched alkyl group, and at least one of R ¹
Is an alicyclic hydrocarbon group or a derivative thereof,
Alternatively, any two R ¹ 's are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atoms to which they are bonded, and the remaining R ^{1's are} Is a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof. ]

[0010]

[Chemical 5]

[General formula (2-1) and general formula (2-
In 2), Y represents a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched divalent hydrocarbon group having 1 to 15 carbon atoms, each R ³
Each independently represent a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, or any 2
R ³ 's are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atoms to which they are bonded, and the remaining R ^3's have 1 carbon atoms.
To a linear or branched alkyl group having 4 to 4 or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or three R ³ are bonded to each other to form a bond. 1 with 4 to 20 carbon atoms along with
A monovalent alicyclic hydrocarbon group or a derivative thereof, and each R ⁴ is independently of each other a monovalent alicyclic hydrocarbon group or a derivative thereof having 4 to 20 carbon atoms, or 1 to 4 carbon atoms.
A straight-chain or branched alkyl group, or any two R ^{4 s} are bonded to each other to form a divalent alicyclic carbon atom having 4 to 20 carbon atoms together with the carbon atoms to which they are bonded. A hydrogen group or its derivative is formed, and the remaining R ⁴
Is a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or three R ⁴ are bonded to each other. , 4 carbons with the carbon atom to which each is attached
To 20 monovalent alicyclic hydrocarbon groups or derivatives thereof are formed. ] It is achieved by.

The present invention will be described in detail below. Component (A) The component (A) in the present invention is a repeating unit represented by the above general formula (1-1) (hereinafter, “repeating unit (1-1)”).
Say. ) And a repeating unit represented by the general formula (1-2) (hereinafter referred to as “repeating unit (1-2)”), and is alkali-insoluble or sparingly alkali-soluble, which is alkali-soluble by the action of an acid. Resin (hereinafter, "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.

The resin (A) preferably further has a repeating unit represented by the following general formula (1-3) (hereinafter referred to as "repeating unit (1-3)").

[0014]

[Chemical 6] [In the general formula (1-3), R ² represents a hydrogen atom or a methyl group, X represents a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, and A represents an oxygen atom or sulfur. A monovalent polar group having at least one atom from the group of atoms and nitrogen atoms is shown. ]

[0015] In general formula (1-1), carbon monovalent alicyclic hydrocarbon group and any two of R ¹ is formed by bonding mutually the carbon number 4 to 20 R ¹ 4 to 20 As the divalent alicyclic hydrocarbon group of, for example, norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane,
Groups consisting of alicyclic rings derived from cycloalkanes such as cycloheptane and cyclooctane; groups consisting of these alicyclic rings are, for example, methyl group, ethyl group, n-propyl group, i-propyl group. 1, a n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl group and the like, which is a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.
Examples thereof include groups substituted with one or more species or with one or more species. Of these alicyclic hydrocarbon groups, a group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane or adamantane, or a group consisting of these alicyclic rings was substituted with the alkyl group. A group and the like are preferable.

Examples of the alicyclic hydrocarbon group derivative include a hydroxyl group; a carboxyl group; an oxo group (ie, = 0 group); a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group. C1-C4 such as 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group Hydroxyalkyl group; methoxy group, ethoxy group, n-propoxy group, i-
C1-C4 alkoxyl groups such as propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group; cyano group; cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl Base, 4-
Examples thereof include a group having at least one kind of a substituent such as a cyanoalkyl group having a carbon number of 2 to 5, such as a cyanobutyl group, or a group having at least one substituent. Of these substituents, hydroxyl group, carboxyl group, hydroxymethyl group, cyano group,
A cyanomethyl group and the like are preferable.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ¹ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 -Methylpropyl group, 1-methylpropyl group, t
A butyl group and the like. Of these alkyl groups, a methyl group and an ethyl group are preferred.

The group --COOC in the general formula (1-1)
(R ¹ ) ₃ is an acid-dissociable group that is dissociated by the action of an acid to form a carboxyl group. Hereinafter, this group is referred to as an acid dissociable group (i). Specific examples of the preferred acid-dissociable group (i) include t-butoxycarbonyl group and groups of the following formulas (i-1) to (i-49).

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

[0026]

[Chemical 14]

[0027]

[Chemical 15]

[0028]

[Chemical 16]

[0029]

[Chemical 17]

[0030]

[Chemical 18]

[0031]

[Chemical 19]

[0032]

[Chemical 20]

[0033]

[Chemical 21]

[0034]

[Chemical formula 22]

Among these acid dissociable groups (i), t-butoxycarbonyl group, formula (i-1), formula (i-2), formula (i-10), formula (i-11), Formula (i-13), Formula (i-14), Formula (i-16), Formula (i-17), Formula (i-34), Formula (i-35), Formula (i-40), Formula Group of (i-41), formula (i-43), formula (i-45), formula (i-46), formula (i-47), formula (i-48) or formula (i-49), etc. Is preferred. In the resin (A), the repeating unit (1
-1) can exist individually or in 2 or more types. Repeating unit (1-1) is the corresponding bicyclo [2.
2.1] A repeating unit derived from a hept-2-ene derivative.

Next, the repeating unit (1-2) is a repeating unit derived from maleic anhydride. Next, in the general formula (1-3), examples of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms of X or a derivative thereof include, for example, the carbon of R ¹ in the general formula (1-1). Number 4 to 2 of 2
The same groups as those exemplified for the valent alicyclic hydrocarbon group or its derivative can be mentioned. Among these alicyclic hydrocarbon groups or derivatives thereof, a group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane or adamantane, a group consisting of these alicyclic rings is the above alkyl group. Substituted groups, groups in which these groups are substituted with one or more of a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, or a cyanomethyl group, and the like are preferable.

The monovalent polar group having at least one atom of the group of oxygen atom, sulfur atom and nitrogen atom of A is, for example, hydroxyl group; carboxyl group;
Oxo group (ie, = 0 group); hydroxymethyl group, 1-
Hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-
Hydroxypropyl group, 1-hydroxybutyl group, 2-
Hydroxyalkyl group having 1 to 4 carbon atoms such as hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group; methoxy group, ethoxy group, n-propoxy group, i
-C1-C4 alkoxyl groups such as propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group; mercapto group; mercaptocarbonyl group; = S group; mercaptomethyl group , 1-mercaptoethyl group, 2-mercaptoethyl group, 1-mercaptopropyl group, 2-mercaptopropyl group, 3-mercaptopropyl group, 1-mercaptobutyl group, 2-mercaptobutyl group, 3-mercaptobutyl group, 4 -C1-C4 mercaptoalkyl group such as mercaptobutyl group; methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, 2-methylpropylthio group, 1-methylpropylthio group , A C1-C4 alkylthio group such as t-butylthio group; cyano group; cyanomethyl group 2-cyanoethyl, 3-cyanopropyl group, and the like can be given cyanoalkyl group having 2 to 5 carbon atoms such as 4-cyanobutyl group.

Of these monovalent polar groups, hydroxyl group, carboxyl group, oxo group, hydroxymethyl group, cyano group, cyanomethyl group and the like are preferable. The repeating unit (1-3) is a repeating unit derived from the corresponding (meth) acrylic acid derivative.

The resin (A) contains 1 repeating unit (hereinafter referred to as "other repeating unit") other than the repeating unit (1-1), the repeating unit (1-2) and the repeating unit (1-3).
It is possible to have more than one species. Examples of the polymerizable unsaturated monomer that gives another repeating unit include, for example, norbornyl (meth) acrylate, isobornyl (meth) acrylate,
Tricyclodecanyl (meth) acrylate, tetracyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate,
(Meth) acrylic acid esters having a bridged hydrocarbon skeleton such as 3-hydroxyadamantyl (meth) acrylate and adamantylmethyl (meth) acrylate;
Carboxyl group-containing esters of unsaturated carboxylic acids such as carboxynorbornyl acrylate, carboxytricyclodecanyl (meth) acrylate, and carboxytetracyclodecanyl (meth) acrylate having a bridged hydrocarbon skeleton;

Norbornene (ie bicyclo [2.2.
1] hept-2-ene), 5-methylbicyclo [2.
2.1] Hept-2-ene, 5-ethylbicyclo [2.
2.1] Hept-2-ene, 5-n-propylbicyclo
[2.2.1] Hept-2-ene, 5-n-butylbicyclo [2.2.1] hept-2-ene, 5-n-pentylbicyclo [2.2.1] hept-2-ene , 5-n-
Hexylbicyclo [2.2.1] hept-2-ene, 5
-Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-methyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en, 8
-Ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8-n-propyl tetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en, 8
-N-butyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] Dodeca-3-ene, 8-n-pentyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en,
8-n-hexyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodec-3-ene, 8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en,
8-Hydroxymethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodeca-3-en,

8-fluorotetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] dodec-3-ene, 8-difluoromethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-pentafluoroethyl tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene, 8,8-difluorotetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,8-bis (trifluoromethyl)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca
3-ene, 8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-trifluoromethyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en,

8,8,9-trifluorotetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en, 8,
8,9-Tris (trifluoromethyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en, 8,
8,9,9-Tetrafluorotetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8, 8, 9,
9-tetrakis (trifluoromethyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en, 8,
8-difluoro-9,9-bis (trifluoromethyl)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca
3-ene, 8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8,8,9-trifluoro-
9-trifluoromethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene, 8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en,

8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodec-3-ene, 8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca
3-ene, 8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en, 8-
Chloro-8,9,9-trifluorotetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8,9-
Dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8- (2 ', 2', 2'-trifluorocarboethoxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-methyl-8- (2 ', 2', 2 '
-Trifluorocarboethoxy) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-en,

Dicyclopentadiene, tricyclo [5.
2.1.0 ^2,6 ] deca-8-ene, tricyclo [5.
2.1.0 ^2,6 ] Deca-3-ene, tricyclo [4.
4.0.1 ^2,5 ] Undec-3-ene, tricyclo [
6.2.1.0 ^1,8 ] Undeca-9-ene, tricyclo
[6.2.1.0 ^1,8 ] Undec-4-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] Dodeca
3-ene, 8-methyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 . 0 ^1,6 ] dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,12 ] dodeca-3-ene, 8-ethylidene tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodeca-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4-ene, pentacyclo [7.4.0.1
^2,5 . 1 ^9,12 . 0 ^8,13] pentadeca-3 other monofunctional monomer having a bridged hydrocarbon skeleton such as ene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate, (meth) acrylic acid 1-methylpropyl, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclo (meth) acrylate Propyl, (meta)
Cyclopentyl acrylate, cyclohexyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, 2-cyclohexyloxycarbonylethyl (meth) acrylate, (meth) acrylic acid 2-
(Meth) acrylic acid esters having no bridged hydrocarbon skeleton such as (4-methoxycyclohexyl) oxycarbonylethyl;

Methyl α-hydroxymethyl acrylate,
α-Hydroxymethylacrylic acid esters such as ethyl α-hydroxymethyl acrylate, n-propyl α-hydroxymethyl acrylate, and n-butyl α-hydroxymethyl acrylate; (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile Unsaturated nitrile compounds such as, malein nitrile, fumaro nitrile, mesacone nitrile, citracone nitrile, and itacone nitrile; Unsaturated amide compounds such as itacone amide; other inclusions such as N- (meth) acryloylmorpholine, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine, vinylimidazole Elemental vinyl compounds; unsaturated carboxylic acids (anhydrides) such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, 4-carboxycyclohexyl (meth) acrylate Carboxyl group-containing esters of unsaturated carboxylic acids, such as, having no bridged hydrocarbon skeleton;

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-butoxycarbonylmethoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-tetrahydrofura Nyloxycarbonyl-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;

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-butyrolactone, α, α-dimethyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-Methoxy-β- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-δ-
Monofunctional monomers such as (meth) acryloyloxylactone compounds that do not have an acid dissociable group such as mevalonolactone,

1,2-adamantanediol di (meth)
Polyfunctionality having a bridged hydrocarbon skeleton such as acrylate, 1,3-adamantane diol di (meth) acrylate, 1,4-adamantane diol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate Monomer;

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-hexane Diol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
A polyfunctional monomer having no bridged hydrocarbon skeleton such as 1,4-bis (2-hydroxypropyl) benzenedi (meth) acrylate and 1,3-bis (2-hydroxypropyl) benzenedi (meth) acrylate Mention may be made of polyfunctional monomers such as the body.

In the resin (A), the repeating unit (1-
The content of 1) is usually 15 to 15 with respect to all repeating units.
It is 50 mol%, preferably 20 to 50 mol%, more preferably 25 to 50 mol%. In this case, if the content of the repeating unit (1-1) is less than 15 mol%, the resolution as a resist tends to be lowered, while if it exceeds 50 mol%, the polymerizability and yield at the time of producing the resin are increased. Tends to decrease. The content of the repeating unit (1-2) is
It is usually from 15 to 50 mol%, preferably from 20 to 50 mol%, more preferably from 25 to 50, based on all repeating units.
Mol%. In this case, when the content of the repeating unit (1-2) is less than 15 mol%, the polymerizability during the production of the resin tends to decrease and the developability as a resist tends to decrease, while the content of 50 mol% tends to decrease. When it exceeds%, the polymerizability and the yield at the time of producing the resin tend to be lowered. The content of the repeating unit (I-3) is
Usually, it is 30 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less. In this case, if the content of the repeating unit (1-3) exceeds 30 mol%, the resolution and developability of the resist tend to be lowered.
Furthermore, the content of other repeating units is usually 30 mol% or less, preferably 25 mol% or less, based on all repeating units.

The resin (A) includes, for example, a polymerizable unsaturated monomer corresponding to each repeating unit thereof, a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds. Can be used to polymerize in a suitable solvent in the presence of a chain transfer agent, if necessary. Examples of the solvent used in the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, Cycloalkanes such as norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; ethyl acetate , N-butyl acetate, i-butyl acetate,
Saturated carboxylic acid esters such as methyl propionate; 2
Examples include ketones such as -butanone, 4-methyl-2-pentanone, and 2-heptanone; and ethers such as tetrahydrofuran, dimethoxyethanes, and diethoxyethanes. These solvents may be used alone or in admixture of two or more. The reaction temperature in the polymerization is usually 40 to 120 ° C, preferably 5
0 to 90 ° C., the reaction time is usually 1 to 48 hours,
It is preferably 1 to 24 hours.

The polystyrene equivalent weight average molecular weight (hereinafter referred to as "Mw") of the resin (A) by gel permeation chromatography (GPC) is usually 3,000.
0 to 30,000, preferably 5,000 to 30,000
It is 0, more preferably 5,000 to 20,000. In this case, when the Mw of the resin (A) is less than 3,000, the heat resistance when used as a resist tends to decrease, while when it exceeds 30,000, the developability when used as a resist tends to decrease. is there. In addition, M of resin (A)
w and gel permeation chromatography (GPC)
Polystyrene-reduced number average molecular weight (hereinafter "Mn")
Say. The ratio (Mw / Mn) is usually 1 to 5, preferably 1 to 3. It is preferable that the resin (A) contain less impurities such as halogens and metals, so that 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 chemical purification methods such as washing with water and liquid extraction, and chemical purification methods and ultrafiltration,
Examples thereof include a combination with a physical purification method such as centrifugation.

Component (B) The component (B) in the present invention comprises a radiation-sensitive acid generator that generates an acid upon exposure (hereinafter referred to as “acid generator (B)”). Examples of the acid generator (B) include onium salt compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds. Below, the example of these acid generators (B) is given. Onium salt compound: Examples of the onium salt compound include iodonium salts, sulfonium salts (including thiophenium salts), phosphonium salts, diazonium salts, pyridinium salts and the like. Examples of preferable onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, and bis. (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n- Butanesulfonate, triphenylsulfonium perfluoro-n-
Octane sulfonate,

Cyclohexyl-2-oxocyclohexylmethylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) Tetrahydrothiophenium nonafluoro-n-butane sulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4
-Methylphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-methylphenyl) tetrahydrothiophenium perfluoro-n
-Octanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane Sulfonate, 1- (4-n
-Butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-
(4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate and the like can be mentioned.

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds. Examples of preferable sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane. Sulfonic acid compound: Examples of the sulfonic acid compound include alkyl sulfonic acid ester, alkyl sulfonic acid imide, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, and imino sulfonate. Preferred sulfonic acid compounds include, for example, benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-
9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.
1] Hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.
1] hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide nonafluoro-n-butanesulfonate, N-hydroxysuccinimide perfluoro- n-octane sulfonate, 1,8-
Examples thereof include naphthalenedicarboxylic acid imide trifluoromethane sulfonate, 1,8-naphthalenedicarboxylic acid imido nonafluoro-n-butane sulfonate, and 1,8-naphthalenedicarboxylic acid imide perfluoro-n-octane sulfonate.

Among these acid generators (B), diphenyliodonium nonafluoro-n-butane sulfonate, diphenyliodonium perfluoro-n-octane sulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butane Sulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octane sulfonate, triphenylsulfonium nonafluoro-n-butane sulfonate, triphenylsulfonium perfluoro-n-octane sulfonate, 1- (3,5-dimethyl -4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butane sulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octance Honeto, 1- (4-n-butoxy-1-yl) tetrahydrothiophenium nonafluoro -n- butane sulfonate, 1- (4-
n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate,

Nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.2.1] hept-5-ene -2,3-dicarbodiimide, N-hydroxysuccinimide nonafluoro-n-butane sulfonate, N-hydroxysuccinimide perfluoro-n-octane sulfonate and the like are preferable. The acid generator (B) may be used alone or in combination of two or more.

The amount of the acid generator (B) used in the present invention is usually 0.1 with respect to 100 parts by weight of the resin (A) from the viewpoint of ensuring sensitivity and developability as a resist.
-20 parts by weight, preferably 0.5-10 parts by weight.
In this case, if the amount of the acid generator (B) used is less than 0.1 part by weight, the sensitivity and the developability tend to be lowered, while 2
If it exceeds 0 parts by weight, the transparency to radiation is lowered, and it tends to be difficult to obtain a rectangular resist pattern.

Component (C) The component (C) in the present invention comprises a compound represented by the above general formula (2-1) or general formula (2-2) and having a molecular weight of 1,000 or less. Hereinafter, the compound represented by the general formula (2-1) having a molecular weight of 1,000 or less is referred to as "compound (C
1) ”, which is represented by the general formula (2-2).
A compound of 000 or less is referred to as "compound (C2)".

General formula (2-1) and general formula (2-2)
In the above, examples of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms of Y or a derivative thereof include, for example, norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, Groups consisting of alicyclic rings derived from cycloalkanes such as cyclooctane; groups consisting of these alicyclic rings include, for example, methyl group, ethyl group, n-
1 of a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group. Examples thereof include groups substituted with one or more species or with one or more species. Of these divalent alicyclic hydrocarbon groups, a group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane or adamantane, or a group consisting of these alicyclic rings is the alkyl group. A group substituted with is preferred.

Examples of the derivative of a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms for Y include, for example, hydroxyl group; carboxyl group; oxo group (ie, = 0 group); hydroxymethyl group, 1 -Hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxy 1 to 1 carbon atoms such as butyl
A hydroxyalkyl group of 4; a methoxy group, an ethoxy group,
C1-C4 alkoxyl groups such as n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group; cyano group; cyanomethyl group, 2- Cyanoethyl group,
Examples thereof include a group having at least one kind or a group having at least one substituent such as a cyanoalkyl group having 2 to 5 carbon atoms such as a 3-cyanopropyl group and a 4-cyanobutyl group. Of these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, a cyanomethyl group and the like are preferable.

Examples of the linear or branched divalent hydrocarbon group having 1 to 15 carbon atoms of Y include, for example, methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group. , Hexamethylene group, 2,5-dimethyl-2,5-hexylene group and the like. Of these divalent hydrocarbon groups, tetramethylene group, 2,5-dimethyl-2,5-hexylene group and the like are preferable.

In addition, R ³ and R ⁴ are monovalent alicyclic hydrocarbon groups having 4 to 20 carbon atoms, the number of carbon atoms formed by bonding any two R ³ or any two R ⁴ to each other. 4 to 2
A divalent alicyclic hydrocarbon group of 0, and three R ³ or three R ⁴ bonded to each other having 4 to 20 carbon atoms
As the monovalent alicyclic hydrocarbon group of, for example,
Norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane,
A group consisting of an alicyclic ring derived from cycloalkanes such as cyclohexane, cycloheptane, cyclooctane; a group consisting of these alicyclic rings is, for example, a methyl group, an ethyl group, an n-propyl group, i Propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t
Examples thereof include a group substituted with one or more linear or branched or cyclic alkyl groups having 1 to 4 carbon atoms such as a -butyl group or a group substituted with one or more. Of these alicyclic hydrocarbon groups, a group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane or adamantane, or a group consisting of these alicyclic rings was substituted with the alkyl group. A group and the like are preferable.

The derivatives of the alicyclic hydrocarbon group include, for example, hydroxyl group; carboxyl group; oxo group (that is, = 0 group); hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group. C1-C4 such as 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group Hydroxyalkyl group; methoxy group, ethoxy group, n-propoxy group, i-
C1-C4 alkoxyl groups such as propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group; cyano group; cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl Base, 4-
Examples thereof include a group having at least one kind of a substituent such as a cyanoalkyl group having a carbon number of 2 to 5, such as a cyanobutyl group, or a group having at least one substituent. Of these substituents, hydroxyl group, carboxyl group, hydroxymethyl group, cyano group,
A cyanomethyl group and the like are preferable.

Examples of the linear or branched alkyl group having 1 to ⁴ carbon atoms of R ³ and R ⁴ are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n- Examples thereof include a butyl group, a 2-methylpropyl group, a 1-methylpropyl group and a t-butyl group. Of these alkyl groups, a methyl group and an ethyl group are preferred.

Preferred specific examples of the compound (C1) include compounds represented by the following formulas (C1-1) to (C1-53).

[0069]

[Chemical formula 23]

[0070]

[Chemical formula 24]

[0071]

[Chemical 25]

[0072]

[Chemical formula 26]

[0073]

[Chemical 27]

[0074]

[Chemical 28]

[0075]

[Chemical 29]

[0076]

[Chemical 30]

[0077]

[Chemical 31]

[0078]

[Chemical 32]

[0079]

[Chemical 33]

[0080]

[Chemical 34]

[0081]

[Chemical 35]

[0082]

[Chemical 36]

[0083]

[Chemical 37]

[0084]

[Chemical 38]

[0085]

[Chemical Formula 39]

[0086]

[Chemical 40]

[0087]

[Chemical 41]

[0088]

[Chemical 42]

[0089]

[Chemical 43]

[0090]

[Chemical 44]

[0091]

[Chemical formula 45]

[0092]

[Chemical formula 46]

[0093]

[Chemical 47]

[0094]

[Chemical 48]

[0095]

[Chemical 49]

[0096]

[Chemical 50]

[0097]

[Chemical 51]

Of these compounds (C1),
(C1-8), (C1-9), (C1-21), (C1-
22), (C1-25), (C1-26), (C1-30),
(C1-31), (C1-43), (C1-47), (C1-
Compounds represented by 48) or (C1-52) are preferable.

Further, preferred specific examples of the compound (C2) include compounds represented by the following formulas (C2-1) to (C2-17).

[0100]

[Chemical 52]

[0101]

[Chemical 53]

[0102]

[Chemical 54]

[0103]

[Chemical 55]

[0104]

[Chemical 56]

[0105]

[Chemical 57]

[0106]

[Chemical 58]

[0107]

[Chemical 59]

[0108]

[Chemical 60]

Of these compounds (C2), the compounds represented by formula (C2-7), formula (C2-13) or formula (C2-17) are particularly preferable.

The compound (C1) is, for example, in the case of di-t-butyl 1,3-adamantanedicarboxylic acid, 1,3-adamantanedicarboxylic acid is dissolved in tetrahydrofuran under a nitrogen atmosphere and trifluoromethane is added to this solution. Acetic anhydride was added dropwise under ice cooling, and the mixture was stirred at room temperature and then t-
The synthesis can be carried out by dropping a tetrahydrofuran solution of butanol under ice-cooling, and stirring and reacting at room temperature overnight, for example. Further, in the case of di-t-butoxycarbonylmethyl 1,3-adamantanedicarboxylate, 1,3-adamantanedicarboxylic acid and t-butyl bromoacetate are reacted in tetrahydrofuran in the presence of a potassium carbonate catalyst. Can be synthesized by.

The compound (C2) is, for example, 2,5
In the case of dimethyl-2,5-di (1-adamantylcarbonyloxy) hexane, 2,5-dimethyl-2,5-hexanediol is dissolved in tetrahydrofuran under a nitrogen atmosphere, triethylamine is added to this solution, It can be synthesized by dropping adamantanecarboxylic acid chloride under ice-cooling and reacting.

In the present invention, the compound (C1) and the compound (C2) may be used alone or in combination of two or more kinds, and the compound (C1) and the compound (C2) may be used in combination. You can also The total amount of the compound (C1) and the compound (C2) used is 100% by weight of the resin (A).
1 to 30 parts by weight, preferably 1 to parts by weight
-20 parts by weight, particularly preferably 1-15 parts by weight.
In this case, if the total amount used is less than 1 part by weight, the resolution as a resist tends to decrease, while if it exceeds 30 parts by weight, the resolution and developability as a resist tend to decrease.

The radiation-sensitive resin composition of the present invention has an action of controlling the diffusion phenomenon of the acid generated from the acid generator (B) upon exposure in the resist film and suppressing undesired chemical reaction in the unexposed region. It is preferable to add the acid diffusion controller. By blending such an acid diffusion controller, the storage stability of the resulting radiation-sensitive resin composition is further improved, and the resolution as a resist is further improved, and from exposure to heat treatment after exposure. A change in the line width of the resist pattern due to a change in the leaving time (PED) can be suppressed, and a composition having excellent process stability can be obtained. 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 (3)

[0114]

[Chemical formula 61] [In the general formula (3), each R ⁵ is 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. Indicates a group. ]

Examples include compounds represented by the formula (1), compounds having two nitrogen atoms in the same molecule, polyamino compounds and polymers having three or more nitrogen atoms, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds. be able to. Of these nitrogen-containing organic compounds, preferably an amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound,
Particularly preferred are amide group-containing compounds and nitrogen-containing heterocyclic compounds.

Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-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.

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, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole; pyridine, and 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, pyridines such as 2,2 ': 6', 2 "-terpyridine; piperazine, piperazine such as 1- (2-hydroxyethyl) piperazine, 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 and the like can be mentioned.

The acid diffusion control agent may be used alone or in admixture of two or more. The compounding amount of the acid diffusion controller is usually 15 parts with respect to 100 parts by weight of the resin (A).
It is not more than 10 parts by weight, preferably not more than 10 parts by weight, more preferably not more than 5 parts by weight. In this case, if the amount of the acid diffusion controller is more than 15 parts by weight, the sensitivity of the resist and the developability of the exposed area tend to be lowered. If the amount of the acid diffusion controller is less than 0.001 part by weight, the pattern shape and dimensional fidelity of the resist may be reduced depending on the process conditions.

Further, the radiation-sensitive resin composition of the present invention may be blended with a surfactant having an effect of improving coating property, developability and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene. In addition to nonionic surfactants such as glycol distearate, KP341 (produced by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, the same No. 95
(Manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, E
F303, EF352 (Tochem Products Co., Ltd.)
Made), Megafax F171, same F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, same F
C431 (Sumitomo 3M Limited), Asahi Guard A
G710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, S
Examples thereof include C-105 and SC-106 (manufactured by Asahi Glass Co., Ltd.). These surfactants may be used alone or in admixture of two or more. The compounding amount of the surfactant is 1 in total of the resin (A) and the acid generator (B).
It is usually 2 parts by weight or less with respect to 00 parts by weight. Further, as additives other than the above, an antihalation agent,
Adhesion aids, storage stabilizers, defoamers 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 of 5 to 50% by weight, preferably 10 to 25% 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, 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-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 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-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, and 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 is particularly useful as a chemically amplified resist. In the chemically amplified resist, the acid dissociable group in the resin (A) or the polycyclic compound (C) is dissociated by the action of the acid generated from the acid generator (B) upon exposure to form a carboxyl group. As a result, the solubility of the exposed portion of the resist in the alkali developing solution is increased, and the exposed portion is dissolved by the alkali developing solution,
Then, the positive resist pattern is obtained. 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 a wafer, and after a heat treatment (hereinafter referred to as “PB”) in some cases, the resist film is formed so as to form a predetermined resist pattern. Expose. As the radiation used at that time, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, etc. are appropriately selected and used according to the type of the acid generator (B) used, KrF excimer laser (wavelength 2
48nm), ArF excimer laser (wavelength 193n
m) or F ₂ excimer laser (wavelength 157 nm)
Far ultraviolet rays represented by In the present invention,
It is preferable to perform a heat treatment (hereinafter referred to as “PEB”) after the exposure. The PEB facilitates the dissociation reaction of the acid dissociable group. The PEB heating conditions vary depending on the composition of the radiation-sensitive resin composition, but are usually 30
-200 degreeC, Preferably it is 50-170 degreeC.

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.

[0126]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. All parts are by weight unless otherwise specified. Each measurement / evaluation in Examples and Comparative Examples was carried out in the following manner. Mw: Tosoh Corp. GPC column (G2000HXL 2
, G3000HXL, 1 G4000HXL 1) using a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C. under the analysis conditions, and gel permeation chromatography (GPC) using monodisperse polystyrene as a standard. It was measured. Radiation transmittance: The composition solution was applied onto quartz glass by spin coating, and PB was performed for 60 seconds on a hot plate kept at 90 ° C. for a resist coating having a film thickness of 0.34 μm from the absorbance at a wavelength of 193 nm. The radiation transmittance was calculated and used as a measure of transparency in the deep ultraviolet region.

Sensitivity: As a substrate, ARC25 (Brewer Science) having a film thickness of 820Å on the surface
Manufactured by the company) a silicon wafer (ARC25) with a film formed
Or AR-19 with a thickness of 820Å
pley) film-formed silicon wafer (AR-1
9), each composition solution was applied onto each substrate by spin coating, and PB was performed on a hot plate under the conditions shown in Table 2 to form a resist coating having a film thickness of 0.34 μm. Exposure was performed via a mask pattern using an ArF excimer laser exposure device (lens numerical aperture 0.55, exposure wavelength 193 nm) manufactured by Nikon Corporation. Then, PEB was performed under the conditions shown in Table 2, and then 25% with a 2.38 wt% tetramethylammonium hydroxide aqueous solution.
It was developed at 60 ° C. for 60 seconds, washed with water, and dried to form a positive resist pattern. At this time, the line width is 0.16 μm
1 line and space pattern (1L1S)
The exposure amount formed with a line width of 1 was defined as the optimum exposure amount, and this optimum exposure amount was defined as the sensitivity.

Resolution: The size of the smallest line-and-space pattern (1L1S) that can be resolved with the optimum exposure amount was taken as the resolution. γ value: ArF excimer laser was applied to a resist film having a film thickness of 0.34 μm formed on each substrate in the same manner as the evaluation of sensitivity, and the exposure amount was adjusted to 0. After changing the exposure amount by 1 J / m ^2, the film was developed, washed with water and dried in the same manner as in the sensitivity evaluation, and the residual film ratio at each exposure amount was sequentially measured to obtain the residual film ratio and the exposure amount. A residual film curve showing the relationship of is created. With this residual film curve, the slope from the point where the residual film ratio started to decrease rapidly to the point where the residual film ratio became almost 0 (zero) was calculated, and this slope was used as the γ value to evaluate the contrast. The larger the γ value, the higher the contrast. FIG. 1 shows the residual film curve and the γ value in Example 1.

Synthesis Example 1 5-[(1-methylcyclopentyl) oxycarbonyl] bicyclo [2.2.1] hept-2-ene 25.9
After 3 g, 16.49 g of maleic anhydride, 7.58 g of 5-n-butylbicyclo [2.2.1] hept-2-ene and 50 g of n-butyl acetate were mixed under a nitrogen atmosphere to form a uniform solution. , Dimethyl azobisisovalerate 4.4
1 g was added and polymerization was carried out at 70 ° C. for 6 hours. After that, the reaction solution is cooled, and 100 g of n-butyl acetate is added to form a uniform solution, which is then added dropwise to 500 g of n-heptane to solidify the resin, and the solidified resin is separated by filtration, washed, and then vacuum dried. 40 g of resin (yield 80% by weight)
Got This resin has a Mw of 6,600 and a ¹³ C-
As a result of composition analysis by NMR, 5-[(1-methylcyclopentyl) oxycarbonyl] bicyclo [2.2.
1] Hept-2-ene / maleic anhydride / 5-n-butylbicyclo [2.2.1] hept-2-ene copolymerization molar ratio was 32.5 / 51.2 / 16.3. . This resin is referred to as resin (A-1).

Synthesis Example 2 5-[(1-methylcyclohexyl) oxycarbonyl] bicyclo [2.2.1] hept-2-ene 26.6
9 g, maleic anhydride 16.97 g, 5-ethylbicyclo [2.2.1] hept-2-ene 6.34 g and n-butyl acetate 50 g were mixed under a nitrogen atmosphere to form a uniform solution, and then azobisiso Dimethyl valerate 4.54g
Was added and polymerized at 70 ° C. for 6 hours. After that, the reaction solution is cooled, and 100 g of n-butyl acetate is added to form a uniform solution, which is then added dropwise to 500 g of n-heptane to solidify the resin, and the solidified resin is separated by filtration, washed, and then vacuum dried. Thus, 42 g (yield 84% by weight) of resin was obtained. This resin has an Mw of 6,900, and is ¹³ C-NM.
As a result of composition analysis by R, 5-[(1-methylcyclohexyl) oxycarbonyl] bicyclo [2.2.1] hept-2-ene / maleic anhydride / 5-ethylbicyclo
[2.2.1] Hept-2-ene copolymerization molar ratio is 3
It was 3.2 / 50.8 / 16.0. This resin is referred to as resin (A-2).

Synthesis Example 3 5-[(1-methylcyclopentyl) oxycarbonyl] bicyclo [2.2.1] hept-2-ene 22.5
5 g, maleic anhydride 15.05 g, bicyclo [2.
2.1] Hept-2-ene (4.82 g), 3-hydroxy-1-adamantyl acrylate (7.58 g) and n-butyl acetate (50 g) were mixed under a nitrogen atmosphere to form a uniform solution, and then dimethyl 6 of azobisisovalerate was added. 0.28g was added and it superposed | polymerized at 70 degreeC for 6 hours. After that, the reaction solution is cooled, and 100 g of n-butyl acetate is added to form a uniform solution, which is then added dropwise to 500 g of n-heptane to solidify the resin, and the solidified resin is separated by filtration, washed, and then vacuum dried. Thus, 40 g of resin (yield 80% by weight) was obtained. This resin has an Mw of 6,900, and is ¹³ C-NM.
As a result of composition analysis by R, 5-[(1-methylcyclopentyl) oxycarbonyl] bicyclo [2.2.1] hept-2-ene / maleic anhydride / bicyclo [2.2.
1] Hept-2-ene / 3-hydroxy-1-adamantyl acrylate copolymerization molar ratio is 30.2 / 46.3.
It was /13.8/9.7. This resin is called resin (A-
3)

Synthesis Example 4 5- (2-Methyl-2-adamantyloxycarbonyl) bicyclo [2.2.1] hept-2-ene 28.8
9 g, maleic anhydride 9.89 g, 3-hydroxy-1
11.21 g of adamantyl acrylate and n of acetic acid
-Butyl (50 g) was mixed in a nitrogen atmosphere to form a uniform solution, and then dimethyl azobisisovalerate (4.64 g) was added, followed by polymerization at 70 ° C for 6 hours. After that, the reaction solution is cooled, and 100 g of n-butyl acetate is added to form a uniform solution, which is then added dropwise to 500 g of n-heptane to solidify the resin, and the solidified resin is separated by filtration, washed, and then vacuum dried. Thus, 42 g (yield: 82% by weight) of resin was obtained. This resin has an Mw of 7,200, and is ¹³ C-NM.
As a result of composition analysis by R, 5- (2-methyl-2-adamantyloxycarbonyl) bicyclo [2.2.1] hept-2-ene / maleic anhydride / 3-hydroxy-1
The adamantyl acrylate copolymerization molar ratio is 39.2
/40.7/20.1. This resin is called resin (A
-4)

Examples 1 to 4 and Comparative Example 1 Various evaluations were performed on each composition solution containing the components shown in Table 1. The evaluation results are shown in Table 3. Components other than the resins (A-1) to (A-4) in Table 1 are as follows. Acid generator (B) B-1: 1- (4-n-butoxynaphthalen-1-yl)
Tetrahydrothiophenium nonafluoro-n-butane sulfonate B-2: bis (4-t-butylphenyl) iodonium nonafluoro-n-butane sulfonate B-3: nonafluoro-n-butane sulfonyl bicyclo [
2.2.1] Hept-5-ene-2,3-dicarbodiimide compound (C1) or compound (C2) C-1: 1,3-adamantanedicarboxylate di-t-butyl (the above formula (C1-8 )) C-2: 2,7-dimethyl-2,7-di (1-adamantylcarbonyloxy) octane (see the above formula (C2-17))

Acid diffusion control agent D-1: Nt-butoxycarbonyl-2-phenylbenzimidazole D-2: Nt-butoxycarbonyldicyclohexylamine Solvent E-1: Propylene glycol monomethyl ether acetate E-2: 2 -Heptanone E-3: cyclohexanone

[0135]

[Table 1]

[0136]

[Table 2]

[0137]

[Table 3]

[0138]

INDUSTRIAL APPLICABILITY The radiation-sensitive resin composition of the present invention has an actinic radiation such as ArF excimer laser (wavelength 193n).
m), a chemically amplified resist sensitive to deep ultraviolet rays represented by a KrF excimer laser (wavelength 248 nm) or F ₂ excimer laser (wavelength 157 nm), which has a particularly high contrast and can form a fine resist pattern with high accuracy. Moreover, transparency, sensitivity to radiation,
It has excellent resolution, storage stability, dry etching resistance, and good adhesion to substrates. It can be used very suitably for the manufacture of semiconductor devices, which are expected to be further miniaturized in the future. .

[Brief description of drawings]

FIG. 1 is a diagram showing a residual film curve and a γ value in Example 1.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 232/08 C08F 232/08 G03F 7/004 501 G03F 7/004 501 H01L 21/027 H01L 21/30 502R (71) Applicant 390009531 International Business Machines Corporation INTERNATIONAL BUSIN ESS MASCHINES COLOR RATION USA 10504, Armonk New Orchard Road, NY (72) Inventor Nishimura, Yukio Tsukiji, Chuo-ku, Tokyo 2-11-24 J S. Incorporated (72) Inventor Michiaki Hoshi 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Incorporated (72) Inventor Seiyano Ya, 2-11-24, Tsukiji, Chuo-ku, Tokyo JSR Corporation (72) Inventor Toru Kajita 2-11-24, Tsukiji, Chuo-ku, Tokyo JSR Corporation (72) Inventor Robert D. Allen California 95120 San Jose Carre del Connejo 6186 (72) Inventor Pushkara Lao Vranacy 12603 Pawkeepsie Sycamore Way 22 F Term (Reference) 2H025 AA01 AA02 AB16 AC04 AC08 AD03 BE00 BE10 BG00 CB08 CB10 CB41 CB45 CC20 FA17 4J100 AK32Q AL08R AR11P BA03P BA03R BA04P BA04R BA05P BA05R BA06P BA06R BA11P BA11R BA15P BA16P BA16R BA40P BA40R BA52R BA53R BA54R BA55R BC02P BC03P BC04P BC07P BC08P BC09P CA38 CA05 DA05

Claims (2)

[Claims] 1. (A) It has a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (1-2), and exhibits alkali solubility by the action of an acid. Alkali-insoluble or sparingly-soluble resin, (B) radiation-sensitive acid generator, and (C) compound having a molecular weight of 1,000 or less represented by the following general formula (2-1) or general formula (2-2) A radiation-sensitive resin composition comprising: [Chemical 1] [In the general formula (1-1), each R ¹ is independently of the other, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a straight chain or branched chain having 1 to 4 carbon atoms. The alkyl group of R ¹ and at least one of R ¹ is the alicyclic hydrocarbon group or a derivative thereof, or any two R ¹ are bonded to each other, together with the carbon atom to which they are bonded. A divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof is formed, and the remaining R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms or 4 to 20 carbon atoms. It is a monovalent alicyclic hydrocarbon group or a derivative thereof. ] [Chemical 2] [In General Formula (2-1) and General Formula (2-2),
Y represents a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched divalent hydrocarbon group having 1 to 15 carbon atoms, and each R ³ is mutually Independently represent a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, or any two R ^{3 s} are mutually To form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atoms to which each is bonded, and the remaining R ³ is a straight chain having 1 to 4 carbon atoms. A branched or branched alkyl group, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or three R ³ are bonded to each other to form a carbon atom bonded to each. Together with a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or the same Forms a conductor, a monovalent alicyclic hydrocarbon group or its derivative, or a linear or branched alkyl group having 1 to 4 carbon atoms, each R ⁴ is 4 to 20 carbon atoms independently of one another Or any two R ⁴ are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atom to which they are bonded, The remaining R ⁴ has 1 to ⁴ carbon atoms
A linear or branched alkyl group having 4 to 4 carbon atoms
A monovalent alicyclic hydrocarbon group of 20 or a derivative thereof, or three R ⁴ are bonded to each other to form a monovalent alicyclic group having 4 to 20 carbon atoms together with the carbon atoms to which they are bonded. Forming a formula hydrocarbon group or a derivative thereof. ] 2. The radiation-sensitive resin composition according to claim 1, wherein the resin as the component (A) further has a repeating unit represented by the following general formula (1-3). [Chemical 3] [In the general formula (1-3), R ² represents a hydrogen atom or a methyl group, X represents a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, and A represents an oxygen atom or sulfur. A monovalent polar group having at least one atom from the group of atoms and nitrogen atoms is shown. ]