JP2000066404A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain high sensitivity to far UV (a low quantity of exposure energy) and to ensure superior resolution and a superior pattern shape by incorporating a resin having specified repeating units and a radiation sensitive acid generating agent. SOLUTION: The radiation sensitive resin compsn. contains a resin having repeating units formula I and repeating units of formula II and a radiation sensitive acid generating agent. In the formulae, R1 and R2 are each H of methyl. The resin has a specified 3-oxo tert. ester structure of a carboxylic acid in the repeating units of the formula II and the 3-oxo tert. ester structure is readily dissociated in the presence of an acid to form a carboxyl group. The repeating units of the formula I in the resin promote the acid dissociation reaction of the 3-oxo tert. ester structure in the repeating units of the formula II. The phenolic hydroxyl group in each of the repeating units of the formula I must be in the 4-position so that the units produce a high promoting effect.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is particularly suitable as a resist useful for fine processing using various radiations such as charged particles such as electron beams and X-rays in addition to far ultraviolet rays represented by KRF excimer laser. And a radiation-sensitive resin composition.

[0002]

2. Description of the Related Art In the field of fine processing represented by the manufacture of integrated circuit elements, the processing size in lithography has been reduced in order to obtain a higher degree of integration. There is a need for a technique capable of performing fine processing with good reproducibility. Therefore, even in resists used for microfabrication, 0.5 μm
It is necessary to form a pattern with a size of 0.5 m or less with high precision, but in the conventional method using visible light (wavelength 800 to 400 nm) or near ultraviolet light (wavelength 400 to 300 nm), a fine pattern of 0.5 μm or less can be formed with high precision. Is extremely difficult to form. Therefore, a shorter wavelength (wavelength 3
The use of radiation (less than 00 nm) is being studied earnestly.
Examples of such short-wavelength radiation include X-rays such as far-ultraviolet rays and synchrotron radiation typified by the emission line spectrum of a mercury lamp (wavelength 254 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and the like. Although a charged particle beam such as an electron beam and an electron beam can be used, lithography using an excimer laser is particularly attracting attention because of its high output and high efficiency characteristics. For this reason, resists used in lithography are required to be able to form fine patterns of 0.5 μm or less with high sensitivity, high resolution, and high reproducibility by excimer laser. As a resist suitable for deep ultraviolet rays such as excimer laser, a radiation-sensitive acid generator that generates an acid by irradiation with radiation (hereinafter referred to as “exposure”) is used, and the sensitivity of the resist is increased by the catalytic action of the acid. An improved “chemically amplified resist” has been proposed. Examples of such a chemically amplified resist include, for example, JP-A-59-1984.
No. 45439 discloses a combination of a resin protected with a t-butyl group or a t-butoxycarbonyl group and a radiation-sensitive acid generator, and JP-A-60-52845 discloses a combination of a resin protected with a silyl group. JP-A-2-25850 discloses a combination of a radiation-sensitive acid generator with a resin having an acetal group and a radiation-sensitive acid generator. However, when the design dimensions of the device become sub-half micron or less, the conventional resin component
It has become impossible to provide a sufficient dissolution contrast required for fine processing. More recently, Japanese Patent Application Laid-Open No. 8-30
Japanese Patent No. 5023 discloses a resist containing a resin protected with a 3-oxo-tertiary alkyl group and a radiation-sensitive acid generator, and the resin component in the resist is various (co). Including polymers, and also in terms of effectiveness, the flexibility of resist materials and adhesion to substrates have only been studied. I am not satisfied with the pattern shape.

[0003]

SUMMARY OF THE INVENTION In view of the situation in the prior art, it is an object of the present invention to provide various types of radiation, in particular, K radiation.
An object of the present invention is to provide a radiation-sensitive resin composition which has high sensitivity (low exposure energy amount) to far ultraviolet rays represented by an RF excimer laser, and can provide excellent resolution performance and pattern shape.

[0004]

According to the present invention, the above-mentioned object firstly comprises (A) a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): It is achieved by a radiation-sensitive resin composition comprising a resin and (D) a radiation-sensitive acid generator.

According to the present invention, the above-mentioned problem is secondly solved.
(A) a resin having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); (B) a repeating unit represented by the following formula (1) and the following formula (3) And (D) a radiation-sensitive resin composition containing a radiation-sensitive acid generator.

[0006] According to the present invention, the above-mentioned problem is, thirdly,
(C) a resin having a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3), and (D) generation of a radiation-sensitive acid And a radiation-sensitive resin composition comprising:

[0007]

Embedded image

[In the formula (1), R ¹ represents a hydrogen atom or a methyl group. ]

[0009]

Embedded image

[In the formula (2), R ² represents a hydrogen atom or a methyl group. ]

[0011]

Embedded image

[In the formula (3), R ³ and R ⁴ independently represent a hydrogen atom or a methyl group, R ⁵ represents a linear or branched alkyl group, R ⁶ represents a linear group, It represents a branched or cyclic alkyl group. ]

Hereinafter, the present invention will be described in detail. (A) Component The component (A) in the present invention is a repeating unit represented by the above formula (1) (hereinafter, referred to as “repeating unit (1)”).
And a repeating unit represented by the formula (2) (hereinafter, referred to as
This is referred to as “repeating unit (2)”. ), And optionally having another repeating unit (hereinafter, referred to as “other repeating unit (a)”) (hereinafter, referred to as “resin (A)”).
Consists of The resin (A) has a specific 3-oxo tertiary ester structure of a carboxylic acid in the repeating unit (2), and the 3-oxo tertiary ester structure is easily dissociated in the presence of an acid (hereinafter referred to as “resin”). This dissociation is abbreviated as "acid dissociation.") To generate a carboxyl group. In this case, 3
When the oxo tertiary ester structure is a primary or secondary ester structure, acid dissociation cannot be performed as quickly as in the case of a 3-oxo tertiary ester structure. Further, the 3-oxo tertiary ester structure in the resin (A) is different from the t-butyl ester structure,
It is bulky and has a high dissolution inhibiting effect on the alkaline developer of the resin (A) before acid dissociation. As a result, the difference in the dissolution rate between the exposed part and the unexposed part is larger than in the case of the t-butyl ester structure. The dissolution contrast of the radiation-sensitive resin composition in an alkaline developer is increased. In addition, two methyl groups directly bonded to the tertiary carbon atom in the 3-oxo tertiary ester structure in the resin (A) are replaced with a larger alkyl group such as an ethyl group or an i-propyl group.
The use of the above alkyl group is not preferable in terms of resist performance, because the resulting composition has low adhesiveness to a substrate and a fine resist pattern is easily peeled off from the substrate.
Further, the repeating unit (1) in the resin (A) has an action of promoting the acid dissociation reaction of the 3-oxo tertiary ester structure in the repeating unit (2). It is essential that the phenolic hydroxyl group in the repeating unit (1) is located at the 4-position, whereby the resin (A) is compared with the 2- or 3-position.
There is an advantage that the effect of promoting the acid dissociation reaction of the 3-oxo tertiary ester structure therein is large.

Another repeating unit (a) in the resin (A)
Are, for example, styrene, α-methylstyrene,
-Methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t-butoxycarbonyloxystyrene, 4-
t-butoxycarbonylmethyloxystyrene, 4-
Vinyl aromatic compounds such as (2'-t-butoxycarbonylethyloxy) styrene, 4-tetrahydrofuranyloxystyrene, 4-tetrahydropyranyloxystyrene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n- (meth) acrylate
Butyl, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, (meth) acrylic acid n-hexyl,
2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylate
Hydroxypropyl, 3-hydroxypropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate , Dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, adamantyl methyl (meth) acrylate, (meth)
Tetrahydrofuranyl acrylate, tetrahydropyranyl (meth) acrylate, phenyl (meth) acrylate,
Benzyl (meth) acrylate, phenethyl (meth) acrylate,

A monomer represented by the following formula (4):

[0017]

Embedded image

A monomer represented by the following formula (5):

[0019]

Embedded image

(Meth) acrylates such as;

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and cinnamic acid;
Carboxyalkyl esters of unsaturated carboxylic acids such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate; (meth) acrylonitrile,
unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, unsaturated amide compounds such as crotonamide, maleamide, fumaramide; Unsaturated imide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide; N-vinyl-ε-caprolactam, N-vinylpyrrolidone, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, A unit in which a polymerizable unsaturated bond such as another nitrogen-containing vinyl compound such as vinylimidazole is cleaved.

Among these other repeating units (a), styrene, α-methylstyrene, 4-t-butoxystyrene, 4-t-butoxycarbonyloxystyrene,
t-butoxycarbonylmethyloxystyrene, 4-
(2′-t-butoxycarbonylethyloxy) styrene, t-butyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, monomer represented by the formula (4) A unit in which a polymerizable unsaturated bond such as a monomer or a monomer represented by the formula (5) is cleaved is preferable.

In the resin (A), the repeating unit (1),
The repeating unit (2) and the other repeating unit (a) can be present alone or in combination of two or more. In the resin (A), the content of the repeating unit (2) varies depending on the composition of the resin composition and the desired properties as a resist, but is the total of the repeating unit (1) and the repeating unit (2). On the other hand, it is preferably 1 to 50 mol%, more preferably 3 to 40 mol%, and particularly preferably 5 to 35 mol%.
It is. In this case, if the content of the repeating unit (2) is less than 1 mol%, the dissolution contrast as a resist tends to decrease, while if it exceeds 50 mol%, the heat resistance as the resist tends to decrease. The content of the repeating unit (1) is preferably from 10 to 90 mol%, more preferably from 20 to 85 mol%, particularly preferably from 30 to 80 mol%, based on all repeating units. In this case, when the content of the repeating unit (1) is less than 10 mol%,
The accelerating effect of the 3-oxo tertiary ester structure on the acid dissociation reaction may be reduced, and the resolution performance of the resist may be impaired. On the other hand, if it exceeds 90 mol%, the dissolution rate of the resin is too fast and the resist cannot be used. There is a tendency that uneven development is likely to occur in the exposed portion. Further, the content of the other repeating unit (a) is preferably at most 40 mol%, more preferably at most 30 mol%, based on all repeating units.

The resin (A) is prepared, for example, by reacting (a) (meth) acrylic acid chloride with diacetone alcohol to synthesize a monomer corresponding to the repeating unit (2), and then forming p-hydroxystyrene. And / or a method of copolymerizing with p-hydroxy-α-methylstyrene in a conventional manner, wherein (b) the monomer corresponding to the repeating unit (2) is
Acetoxystyrene and / or p-acetoxy-α
After copolymerization with -methylstyrene by a conventional method, the compound can be produced by a method of hydrolyzing an acetyl group by a conventional method using a base such as aqueous ammonia as a catalyst. The resin (A) has a polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “Mw”) by gel permeation chromatography (hereinafter, referred to as “GPC”) of preferably 1,000 to 500,000, and more preferably 2, , 0
00 to 400,000, particularly preferably 3,000 to 3,
00,000. In this case, if the Mw of the resin (A) is less than 1,000, the sensitivity and heat resistance as a resist tend to decrease, while if it exceeds 500,000, the developability as a resist tends to decrease. is there. The ratio (Mw / Mn) of the Mw of the resin (A) to the number average molecular weight in terms of polystyrene by GPC (hereinafter referred to as “Mn”) is usually 1 to 5, preferably 1 to 2.
5 In the present invention, the resin (A) can be used alone or in combination of two or more.

The resin (A) can be used by mixing with another resin having an acid-dissociable group. As the other resin having such an acid dissociable group, the following component (B) is particularly preferable. (B) Component The component (B) in the present invention has a repeating unit (1) and a repeating unit represented by the above formula (3) (hereinafter, referred to as “repeating unit (3)”). (Hereinafter, referred to as “resin (B)”).

The repeating unit (3) in the resin (B) is
It is a unit having a specific acid dissociable acetal group. In the formula (3), examples of the linear or branched alkyl group for R ⁵ include a linear alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Alkyl group; a branched alkyl group having 3 to 4 carbon atoms such as an i-propyl group, an i-butyl group, a sec-butyl group and a t-butyl group can be exemplified. Examples of the linear, branched or cyclic alkyl group for R ⁶ include a methyl group,
Linear alkyl group having 1 to 6 carbon atoms such as ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group; i-propyl group, i-butyl group, sec-butyl Group, t-butyl group, neopentyl group, etc.
And a cyclic alkyl group having 5 to 6 carbon atoms such as a cyclopentyl group and a cyclohexyl group.

As the repeating unit (3), for example, 4-
(1′-methoxyethoxy) styrene, 4- (1′-ethoxyethoxy) styrene, 4- (1′-n-propoxyethoxy) styrene, 4- (1′-i-propoxyethoxy) styrene, 4- (1 '-N-butoxyethoxy) styrene, 4- (1'-t-butoxyethoxy) styrene, 4- (1'-n-pentyloxyethoxy) styrene, 4- (1'-n-hexyloxyethoxy) styrene, 4- (1′-cyclopentyloxyethoxy)
Styrene, 4- (1′-cyclohexyloxyethoxy) styrene, 4- (1′-methoxypropoxy) styrene, 4- (1′-ethoxypropoxy) styrene,
-(1'-n-propoxypropoxy) styrene, 4-
(1′-i-propoxypropoxy) styrene, 4-
(1′-n-butoxypropoxy) styrene, 4-
(1′-t-butoxypropoxy) styrene, 4-
(1′-n-pentyloxypropoxy) styrene, 4
-(1'-n-hexyloxypropoxy) styrene,
4- (1′-cyclopentyloxypropoxy) styrene, 4- (1′-cyclohexyloxypropoxy) styrene,

4- (1'-methoxybutoxy) styrene, 4- (1'-ethoxybutoxy) styrene,
(1′-n-propoxybutoxy) styrene, 4-
(1′-i-propoxybutoxy) styrene, 4-
(1′-n-butoxybutoxy) styrene, 4- (1 ′
-T-butoxybutoxy) styrene, 4- (1'-n-
Pentyloxybutoxy) styrene, 4- (1′-n-
Hexyloxybutoxy) styrene, 4- (1′-cyclopentyloxybutoxy) styrene, 4- (1′-cyclohexyloxybutoxy) styrene, 4- (1′-
Methoxy-2′-methylpropoxy) styrene, 4-
(1′-ethoxy-2′-methylpropoxy) styrene, 4- (1′-n-propoxy-2′-methylpropoxy) styrene, 4- (1′-i-propoxy-2′-)
Methylpropoxy) styrene, 4- (1′-n-butoxy-2′-methylpropoxy) styrene, 4- (1′-
t-butoxy-2'-methylpropoxy) styrene, 4
-(1'-n-pentyloxy-2'-methylpropoxy) styrene, 4- (1'-n-hexyloxy-2 '
-Methylpropoxy) styrene, 4- (1′-cyclopentyloxy-2′-methylpropoxy) styrene,
-(1'-cyclohexyloxy-2'-methylpropoxy) styrene,

4- (1'-methoxypentyloxy) styrene, 4- (1'-ethoxypentyloxy) styrene, 4- (1'-n-propoxypentyloxy) styrene, 4- (1'-i-propoxy) Pentyloxy) styrene, 4- (1′-n-butoxypentyloxy) styrene, 4- (1′-t-butoxypentyloxy) styrene, 4- (1′-n-pentyloxypentyloxy) styrene, 4- (1′-n-hexyloxypentyloxy) styrene, 4- (1′-cyclopentyloxypentyloxy) styrene, 4- (1′-cyclohexyloxypentyloxy) styrene, 4- (1′-methoxy-2 ′, 2′-dimethylpropoxy) styrene,
4- (1′-ethoxy-2 ′, 2′-dimethylpropoxy) styrene, 4- (1′-n-propoxy-2 ′,
2′-dimethylpropoxy) styrene, 4- (1′-i
-Propoxy-2 ', 2'-dimethylpropoxy) styrene, 4- (1'-n-butoxy-2', 2'-dimethylpropoxy) styrene, 4- (1'-t-butoxy-
2 ′, 2′-dimethylpropoxy) styrene, 4-
(1′-n-pentyloxy-2 ′, 2′-dimethylpropoxy) styrene, 4- (1′-n-hexyloxy-2 ′, 2′-dimethylpropoxy) styrene, 4-
(1′-cyclopentyloxy-2 ′, 2′-dimethylpropoxy) styrene, 4- (1′-cyclohexyloxy-2 ′, 2′-dimethylpropoxy) styrene,

4- (1′-methoxyethoxy) -α-methylstyrene, 4- (1′-ethoxyethoxy) -α-
Methylstyrene, 4- (1′-n-propoxyethoxy) -α-methylstyrene, 4- (1′-i-propoxyethoxy) -α-methylstyrene, 4- (1′-n-
(Butoxyethoxy) -α-methylstyrene, 4- (1 ′
-T-butoxyethoxy) -α-methylstyrene, 4-
(1′-n-pentyloxyethoxy) -α-methylstyrene, 4- (1′-n-hexyloxyethoxy)-
α-methylstyrene, 4- (1′-cyclopentyloxyethoxy) -α-methylstyrene, 4- (1′-cyclohexyloxyethoxy) -α-methylstyrene,
-(1′-methoxypropoxy) -α-methylstyrene, 4- (1′-ethoxypropoxy) -α-methylstyrene, 4- (1′-n-propoxypropoxy) -α
-Methylstyrene, 4- (1′-i-propoxypropoxy) -α-methylstyrene, 4- (1′-n-butoxypropoxy) -α-methylstyrene, 4- (1′-t
-Butoxypropoxy) -α-methylstyrene, 4-
(1′-n-pentyloxypropoxy) -α-methylstyrene, 4- (1′-n-hexyloxypropoxy) -α-methylstyrene, 4- (1′-cyclopentyloxypropoxy) -α-methylstyrene, 4-
(1′-cyclohexyloxypropoxy) -α-methylstyrene,

4- (1′-methoxybutoxy) -α-methylstyrene, 4- (1′-ethoxybutoxy) -α-
Methylstyrene, 4- (1′-n-propoxybutoxy) -α-methylstyrene, 4- (1′-i-propoxybutoxy) -α-methylstyrene, 4- (1′-n-
(Butoxybutoxy) -α-methylstyrene, 4- (1 ′
-T-butoxybutoxy) -α-methylstyrene, 4-
(1′-n-pentyloxybutoxy) -α-methylstyrene, 4- (1′-n-hexyloxybutoxy)-
α-methylstyrene, 4- (1′-cyclopentyloxybutoxy) -α-methylstyrene, 4- (1′-cyclohexyloxybutoxy) -α-methylstyrene,
-(1'-methoxy-2'-methylpropoxy) -α-
Methylstyrene, 4- (1′-ethoxy-2′-methylpropoxy) -α-methylstyrene, 4- (1′-n-
Propoxy-2′-methylpropoxy) -α-methylstyrene, 4- (1′-i-propoxy-2′-methylpropoxy) -α-methylstyrene, 4- (1′-n-butoxy-2′-methyl Propoxy) -α-methylstyrene, 4- (1′-t-butoxy-2′-methylpropoxy) -α-methylstyrene, 4- (1′-n-pentyloxy-2′-methylpropoxy) -α- Methylstyrene, 4- (1′-n-hexyloxy-2′-methylpropoxy) -α-methylstyrene, 4- (1′-cyclopentyloxy-2′-methylpropoxy) -α-methylstyrene, 4- ( 1'-cyclohexyloxy-2 '
-Methylpropoxy) -α-methylstyrene,

4- (1'-methoxypentyloxy)-
α-methylstyrene, 4- (1′-ethoxypentyloxy) -α-methylstyrene, 4- (1′-n-propoxypentyloxy) -α-methylstyrene, 4-
(1′-i-propoxypentyloxy) -α-methylstyrene, 4- (1′-n-butoxypentyloxy)
-Α-methylstyrene, 4- (1′-t-butoxypentyloxy) -α-methylstyrene, 4- (1′-n-
Pentyloxypentyloxy) -α-methylstyrene, 4- (1′-n-hexyloxypentyloxy)
-Α-methylstyrene, 4- (1′-cyclopentyloxypentyloxy) -α-methylstyrene, 4-
(1′-cyclohexyloxypentyloxy) -α-
Methylstyrene, 4- (1′-methoxy-2 ′, 2′-
Dimethylpropoxy) -α-methylstyrene, 4-
(1′-ethoxy-2 ′, 2′-dimethylpropoxy)
-Α-methylstyrene, 4- (1′-n-propoxy-
2 ′, 2′-dimethylpropoxy) -α-methylstyrene, 4- (1′-i-propoxy-2 ′, 2′-dimethylpropoxy) -α-methylstyrene, 4- (1′-n
-Butoxy-2 ', 2'-dimethylpropoxy) -α-
Methylstyrene, 4- (1′-t-butoxy-2 ′,
2′-dimethylpropoxy) -α-methylstyrene, 4
-(1′-n-pentyloxy-2 ′, 2′-dimethylpropoxy) -α-methylstyrene, 4- (1′-n-
Hexyloxy-2 ', 2'-dimethylpropoxy)-
α-methylstyrene, 4- (1′-cyclopentyloxy-2 ′, 2′-dimethylpropoxy) -α-methylstyrene, 4- (1′-cyclohexyloxy-2 ′,
2′-dimethylpropoxy) -α-methylstyrene,

4- (1'-methyl-1'-methoxyethoxy) styrene, 4- (1'-methyl-1'-ethoxyethoxy) styrene, 4- (1'-methyl-1'-n-
Propoxyethoxy) styrene, 4- (1′-methyl-
1′-i-propoxyethoxy) styrene, 4- (1 ′
-Methyl-1'-n-butoxyethoxy) styrene, 4
-(1′-methyl-1′-t-butoxyethoxy) styrene, 4- (1′-methyl-1′-n-pentyloxyethoxy) styrene, 4- (1′-methyl-1′-n-)
Hexyloxyethoxy) styrene, 4- (1′-methyl-1′-cyclopentyloxyethoxy) styrene,
4- (1′-methyl-1′-cyclohexyloxyethoxy) styrene, 4- (1′-methyl-1′-methoxypropoxy) styrene, 4- (1′-methyl-1′-ethoxypropoxy) styrene, -(1′-methyl-
1′-n-propoxypropoxy) styrene, 4-
(1′-methyl-1′-i-propoxypropoxy) styrene, 4- (1′-methyl-1′-n-butoxypropoxy) styrene, 4- (1′-methyl-1′-t-butoxypropoxy) Styrene, 4- (1′-methyl-
1′-n-pentyloxypropoxy) styrene, 4-
(1′-methyl-1′-n-hexyloxypropoxy) styrene, 4- (1′-methyl-1′-cyclopentyloxypropoxy) styrene, 4- (1′-methyl-1′-cyclohexyloxypropoxy) styrene ,

4- (1'-methyl-1'-methoxybutoxy) styrene, 4- (1'-methyl-1'-ethoxybutoxy) styrene, 4- (1'-methyl-1'-n-
Propoxybutoxy) styrene, 4- (1′-methyl-
1′-i-propoxybutoxy) styrene, 4- (1 ′
-Methyl-1'-n-butoxybutoxy) styrene, 4
-(1′-methyl-1′-t-butoxybutoxy) styrene, 4- (1′-methyl-1′-n-pentyloxybutoxy) styrene, 4- (1′-methyl-1′-n-)
Hexyloxybutoxy) styrene, 4- (1′-methyl-1′-cyclopentyloxybutoxy) styrene,
4- (1′-methyl-1′-cyclohexyloxybutoxy) styrene, 4- (1 ′, 2′-dimethyl-1′-
Methoxypropoxy) styrene, 4- (1 ′, 2′-dimethyl-1′-ethoxypropoxy) styrene,
(1 ′, 2′-dimethyl-1′-n-propoxypropoxy) styrene, 4- (1 ′, 2′-dimethyl-1′-
i-propoxypropoxy) styrene, 4- (1 ′,
2′-dimethyl-1′-n-butoxypropoxy) styrene, 4- (1 ′, 2′-dimethyl-1′-t-butoxypropoxy) styrene, 4- (1 ′, 2′-dimethyl-1′-) n-pentyloxypropoxy) styrene, 4
-(1 ', 2'-dimethyl-1'-n-hexyloxypropoxy) styrene, 4- (1', 2'-dimethyl-
1′-cyclopentyloxypropoxy) styrene, 4
-(1 ′, 2′-dimethyl-1′-cyclohexyloxypropoxy) styrene,

4- (1'-methyl-1'-methoxypentyloxy) styrene, 4- (1'-methyl-1'-ethoxypentyloxy) styrene, 4- (1'-methyl-1'-n- Propoxypentyloxy) styrene, 4
-(1'-methyl-1'-i-propoxypentyloxy) styrene, 4- (1'-methyl-1'-n-butoxypentyloxy) styrene, 4- (1'-methyl-
1′-t-butoxypentyloxy) styrene, 4-
(1′-methyl-1′-n-pentyloxypentyloxy) styrene, 4- (1′-methyl-1′-n-hexyloxypentyloxy) styrene, 4- (1′-methyl-1′-cyclopentyl) Oxypentyloxy) styrene, 4- (1′-methyl-1′-cyclohexyloxypentyloxy) styrene, 4- (1 ′, 2 ′,
2'-trimethyl-1'-methoxypropoxy) styrene, 4- (1 ', 2', 2'-trimethyl-1'-ethoxypropoxy) styrene, 4- (1 ', 2', 2'-
Trimethyl-1′-n-propoxypropoxy) styrene, 4- (1 ′, 2 ′, 2′-trimethyl-1′-i-
Propoxypropoxy) styrene, 4- (1 ′, 2 ′,
2'-trimethyl-1'-n-butoxypropoxy) styrene, 4- (1 ', 2', 2'-trimethyl-1'-
(t-butoxypropoxy) styrene, 4- (1 ′,
2 ′, 2′-trimethyl-1′-n-pentyloxypropoxy) styrene, 4- (1 ′, 2 ′, 2′-trimethyl-1′-n-hexyloxypropoxy) styrene, 4- (1 ′, 2 ′, 2′-trimethyl-1′-cyclopentyloxypropoxy) styrene, 4- (1 ′,
2 ′, 2′-trimethyl-1′-cyclohexyloxypropoxy) styrene,

4- (1'-methyl-1'-methoxyethoxy) -α-methylstyrene, 4- (1'-methyl-
1′-ethoxyethoxy) -α-methylstyrene, 4-
(1′-methyl-1′-n-propoxyethoxy) -α
-Methylstyrene, 4- (1′-methyl-1′-i-propoxyethoxy) -α-methylstyrene, 4- (1 ′
-Methyl-1′-n-butoxyethoxy) -α-methylstyrene, 4- (1′-methyl-1′-t-butoxyethoxy) -α-methylstyrene, 4- (1′-methyl)
1′-n-pentyloxyethoxy) -α-methylstyrene, 4- (1′-methyl-1′-n-hexyloxyethoxy) -α-methylstyrene, 4- (1′-methyl-1′-cyclopentyl) (Oxyethoxy) -α-methylstyrene, 4- (1′-methyl-1′-cyclohexyloxyethoxy) -α-methylstyrene, 4- (1′-
Methyl-1′-methoxypropoxy) -α-methylstyrene, 4- (1′-methyl-1′-ethoxypropoxy) -α-methylstyrene, 4- (1′-methyl-1 ′
-N-propoxypropoxy) -α-methylstyrene,
4- (1′-methyl-1′-i-propoxypropoxy) -α-methylstyrene, 4- (1′-methyl-1 ′)
-N-butoxypropoxy) -α-methylstyrene, 4
-(1'-methyl-1'-t-butoxypropoxy)-
α-methylstyrene, 4- (1′-methyl-1′-n-
Pentyloxypropoxy) -α-methylstyrene, 4
-(1′-methyl-1′-n-hexyloxypropoxy) -α-methylstyrene, 4- (1′-methyl-1 ′
-Cyclopentyloxypropoxy) -α-methylstyrene, 4- (1′-methyl-1′-cyclohexyloxypropoxy) -α-methylstyrene,

4- (1'-methyl-1'-methoxybutoxy) -α-methylstyrene, 4- (1'-methyl-
1′-ethoxybutoxy) -α-methylstyrene, 4-
(1′-methyl-1′-n-propoxybutoxy) -α
-Methylstyrene, 4- (1′-methyl-1′-i-propoxybutoxy) -α-methylstyrene, 4- (1 ′
-Methyl-1'-n-butoxybutoxy) -α-methylstyrene, 4- (1′-methyl-1′-t-butoxybutoxy) -α-methylstyrene, 4- (1′-methyl-
1′-n-pentyloxybutoxy) -α-methylstyrene, 4- (1′-methyl-1′-n-hexyloxybutoxy) -α-methylstyrene, 4- (1′-methyl-1′-cyclopentyl) Oxybutoxy) -α-methylstyrene, 4- (1′-methyl-1′-cyclohexyloxybutoxy) -α-methylstyrene, 4- (1 ′,
2′-dimethyl-1′-methoxypropoxy) -α-methylstyrene, 4- (1 ′, 2′-dimethyl-1′-ethoxypropoxy) -α-methylstyrene, 4-
(1 ′, 2′-dimethyl-1′-n-propoxypropoxy) -α-methylstyrene, 4- (1 ′, 2′-dimethyl-1′-i-propoxypropoxy) -α-methylstyrene, 4- (1 ′, 2′-dimethyl-1′-n-butoxypropoxy) -α-methylstyrene, 4-
(1 ′, 2′-dimethyl-1′-t-butoxypropoxy) -α-methylstyrene, 4- (1 ′, 2′-dimethyl-1′-n-pentyloxypropoxy) -α-methylstyrene, -(1 ', 2'-dimethyl-1'-n-
Hexyloxypropoxy) -α-methylstyrene, 4
-(1 ′, 2′-dimethyl-1′-cyclopentyloxypropoxy) -α-methylstyrene, 4- (1 ′,
2′-dimethyl-1′-cyclohexyloxypropoxy) -α-methylstyrene,

4- (1′-methyl-1′-methoxypentyloxy) -α-methylstyrene, 4- (1′-methyl-1′-ethoxypentyloxy) -α-methylstyrene, 4- (1 ′ -Methyl-1′-n-propoxypentyloxy) -α-methylstyrene, 4- (1′-methyl-1′-i-propoxypentyloxy) -α-methylstyrene, 4- (1′-methyl-1) '-N-butoxypentyloxy) -α-methylstyrene, 4- (1'-
Methyl-1′-t-butoxypentyloxy) -α-methylstyrene, 4- (1′-methyl-1′-n-pentyloxypentyloxy) -α-methylstyrene, 4-
(1′-methyl-1′-n-hexyloxypentyloxy) -α-methylstyrene, 4- (1′-methyl-
1′-cyclopentyloxypentyloxy) -α-methylstyrene, 4- (1′-methyl-1′-cyclohexyloxypentyloxy) -α-methylstyrene,
-(1 ′, 2 ′, 2′-trimethyl-1′-methoxypropoxy) -α-methylstyrene, 4- (1 ′, 2 ′,
2'-trimethyl-1'-ethoxypropoxy) -α-
Methylstyrene, 4- (1 ′, 2 ′, 2′-trimethyl-1′-n-propoxypropoxy) -α-methylstyrene, 4- (1 ′, 2 ′, 2′-trimethyl-1′-i
-Propoxypropoxy) -α-methylstyrene, 4-
(1 ′, 2 ′, 2′-trimethyl-1′-n-butoxypropoxy) -α-methylstyrene, 4- (1 ′,
2 ′, 2′-trimethyl-1′-t-butoxypropoxy) -α-methylstyrene, 4- (1 ′, 2 ′, 2′-
Trimethyl-1'-n-pentyloxypropoxy)-
α-methylstyrene, 4- (1 ′, 2 ′, 2′-trimethyl-1′-n-hexyloxypropoxy) -α-methylstyrene, 4- (1 ′, 2 ′, 2′-trimethyl-
1′-cyclopentyloxypropoxy) -α-methylstyrene, 4- (1 ′, 2 ′, 2′-trimethyl-1 ′
-Cyclohexyloxypropoxy) styrene and the like, in which a polymerizable unsaturated bond is cleaved.

Of these repeating units (3), 4-
(1′-methoxyethoxy) styrene, 4- (1′-ethoxyethoxy) styrene, 4- (1′-methoxypropoxy) styrene, 4- (1′-ethoxypropoxy)
Styrene, 4- (1′-methoxyethoxy) -α-methylstyrene, 4- (1′-ethoxyethoxy) -α-methylstyrene, 4- (1′-methoxypropoxy) -α
-Methylstyrene, 4- (1'-ethoxypropoxy)
A unit in which a polymerizable unsaturated bond such as -α-methylstyrene is cleaved is preferable.

Other repeating units (a) in the resin (B) include styrene, α-methylstyrene,
t-butoxystyrene, 4-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethyloxystyrene, 4- (2′-t-butoxycarbonylethyloxy) styrene, t-butyl (meth) acrylate,
Isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, a monomer represented by the formula (4),
A unit in which a polymerizable unsaturated bond such as a monomer represented by the formula (5) is cleaved is preferable.

In the resin (B), the repeating unit (1)
The repeating unit (3) and the other repeating unit (a) may be present alone or in combination of two or more. Further, the resin (B) may have a structure partially cross-linked with an appropriate cross-linking group (for example, a cross-linking group having a diethylene glycol skeleton).

In the resin (B), the content of the repeating unit (3) varies depending on the composition of the resin composition and the desired properties as a resist. Is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, and particularly preferably 25 to 45 mol%, based on the total of In this case, if the content of the repeating unit (3) is less than 10 mol%, the resolution performance as a resist tends to decrease, while if it exceeds 60 mol%, the sensitivity as a resist tends to decrease.
The content of the repeating unit (1) is preferably from 10 to 90 mol%, more preferably from 20 to 85 mol%, particularly preferably from 30 to 80 mol%, based on all repeating units. In this case, when the content of the repeating unit (1) is less than 10 mol%, the effect of accelerating the acid dissociation reaction of the 3-oxo tertiary ester structure may be reduced, and the resolution performance as a resist may be impaired. If it exceeds 90 mol%, the dissolution rate of the resin will be too fast, and there will be a tendency for development unevenness to occur in unexposed areas as a resist. Furthermore, the content of other repeating units (a) is
It is preferably at most 40 mol%, more preferably at most 30 mol%.

The resin (B) can be used, for example, in (c) a part of the phenolic hydroxyl group in the (co) polymer of 4-hydroxystyrene and / or 4-hydroxy-α-methylstyrene under a weakly acidic condition. Reacting with vinyl ether compounds such as ethyl vinyl ether, ethylene glycol n-butyl vinyl ether and ethylene glycol cyclohexyl vinyl ether; (d) a part of phenolic hydroxyl groups in 4-hydroxystyrene or 4-hydroxy-α-methylstyrene Is reacted with a vinyl ether compound such as ethyl vinyl ether, ethylene glycol n-butyl vinyl ether, or ethylene glycol cyclohexyl vinyl ether under a weakly acidic condition to synthesize a monomer corresponding to the repeating unit (3). Repeating unit (1) It can be produced by a method of copolymerizing with the corresponding monomer by a conventional method or the like. In the resin (B), the structure partially cross-linked by the cross-linking group having a diethylene glycol skeleton may be used, for example, in the reaction with the vinyl ether compound in the method (c) described above.
It can be introduced by simultaneously reacting an appropriate amount of diethylene glycol divinyl ether.

The Mw of the resin (B) is preferably 1,000.
0 to 500,000, more preferably 3,000 to 2
50,000, particularly preferably 4,000 to 100,0
00. In this case, the Mw of the resin (B) is 1,000.
When the amount is less than the above, the sensitivity and heat resistance of the resist tend to decrease, while when it exceeds 500,000, the developability as the resist tends to decrease. The Mw / Mn of the resin (B) is usually 1 to 5, preferably 1
~ 2.5. In the present invention, the resin (B) can be used alone or in combination of two or more. In the present invention, when the resin (B) is used, its use ratio is preferably from 5 to 95% by weight, more preferably from 10 to 95% by weight, based on the total of the resin (A), the resin (B) and the resin (C). ~ 90% by weight.

Component (C) The component (C) in the present invention comprises a resin having a repeating unit (1), a repeating unit (2) and a repeating unit (3), and optionally having another repeating unit (a) ( Hereinafter, referred to as “resin (C)”). Examples of the repeating unit (3) in the resin (C) include 4- (1′-methoxyethoxy) styrene, 4- (1′-ethoxyethoxy) styrene, 4- (1′-methoxypropoxy) styrene,
(1′-ethoxypropoxy) styrene, 4- (1′-
(Methoxyethoxy) -α-methylstyrene, 4- (1 ′
-Ethoxyethoxy) -α-methylstyrene, 4-
(1′-methoxypropoxy) -α-methylstyrene,
A unit in which a polymerizable unsaturated bond such as 4- (1′-ethoxypropoxy) -α-methylstyrene has been cleaved is preferable.

Other repeating units (a) in the resin (C) include styrene, α-methylstyrene,
t-butoxystyrene, 4-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethyloxystyrene, 4- (2′-t-butoxycarbonylethyloxy) styrene, t-butyl (meth) acrylate,
Isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, a monomer represented by the formula (4),
A unit in which a polymerizable unsaturated bond such as a monomer represented by the formula (5) is cleaved is preferable.

In the resin (C), the repeating unit (1)
Each of the repeating unit (2), the repeating unit (3) and the other repeating unit (a) may be present alone or in combination of two or more. Further, the resin (C) may have a structure partially cross-linked with an appropriate cross-linking group (for example, a cross-linking group having a diethylene glycol skeleton).

In the resin (C), the content of the repeating unit (2) is determined based on the total of the repeating units (1) to (3).
Preferably it is 1 to 45 mol%, more preferably 3 to 40 mol%.
Mol%, particularly preferably 5 to 40 mol%. In this case, when the content of the repeating unit (2) is less than 1 mol%, the resolution performance as a resist tends to decrease.
If it exceeds 5 mol%, the heat resistance of the resist tends to decrease. The content of the repeating unit (3) is preferably 5 to the total of the repeating units (1) to (3).
-45 mol%, more preferably 10-45 mol%, particularly preferably 10-35 mol%. In this case, if the content of the repeating unit (3) is less than 5 mol%, the resolution performance as a resist tends to decrease, while 45 mol%
If it exceeds 300, the sensitivity as a resist tends to decrease. The content of the repeating unit (1) is preferably from 10 to 90 mol%, more preferably from 20 to 85 mol%, particularly preferably from 30 to 80 mol%, based on all repeating units. In this case, the content of the repeating unit (1) is 10
If it is less than mol%, the effect of accelerating the acid dissociation reaction of the 3-oxo tertiary ester structure may be reduced, and the resolution performance as a resist may be impaired. This tends to cause uneven development in unexposed areas as a resist. Further, the content of the other repeating unit (a) is preferably at most 30 mol%, more preferably at most 25 mol%, based on all repeating units.
Mol% or less.

The resin (C) is obtained, for example, by copolymerizing (e) 4-hydroxystyrene and / or 4-hydroxy-α-methylstyrene with a monomer corresponding to the repeating unit (2) by a conventional method. A method of reacting a part of the phenolic hydroxyl groups in the obtained copolymer with a vinyl ether compound such as ethyl vinyl ether, ethylene glycol n-butyl vinyl ether, ethylene glycol cyclohexyl vinyl ether under a weakly acidic condition; ) Each monomer corresponding to the repeating units (1) to (3) can be produced by, for example, a method of copolymerizing by a conventional method. In the resin (C), the structure partially cross-linked by the cross-linking group having a diethylene glycol skeleton is used for the reaction with the vinyl ether compound in the method (e).
For example, it can be introduced by simultaneously reacting an appropriate amount of diethylene glycol divinyl ether. Mw of the resin (C) is preferably 1,000 to 50.
000, more preferably 3,000-250,
000, particularly preferably 4,000 to 150,000. In this case, if the Mw of the resin (C) is less than 1,000, the sensitivity and heat resistance as a resist tend to decrease, while if it exceeds 500,000, the developability as a resist tends to decrease. is there. The Mw / Mn of the resin (C) is usually 1 to 5, preferably 1 to 5.
2.5.

In the present invention, the resin (C) can be used alone or in combination of two or more. Also,
The resin (C) can be used as a mixture with the resin (A) and / or the resin (B), and in some cases, can be used as a mixture with a resin having an acid-labile group. Resin (C) is replaced with resin (A) and / or resin (B)
When used as a mixture with the resin (A), the resin (B) and the total of the resin (C),
Preferably 5-95% by weight, more preferably 10-9%
0% by weight.

Component (D) The component (D) in the present invention comprises a radiation-sensitive acid generator that generates an acid upon exposure (hereinafter, referred to as “acid generator (D)”). Examples of the acid generator (D) include an onium salt compound, a sulfone compound, a sulfonate compound, a sulfonimide compound, and a diazomethane compound. Examples of these acid generators (D) are shown below. Onium salt compound: Examples of the onium salt compound include an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, an ammonium salt, a pyridinium salt and the like. Specific examples of the onium salt compound include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n
-Butanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, bis (t-butylphenyl) iodonium 10-camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium naphthalene Examples thereof include sulfonate, triphenylsulfonium 10-camphorsulfonate, (4-hydroxyphenyl) benzylmethylsulfonium-p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, and diphenyliodonium hexafluoroantimonate. Sulfone compound: Examples of the sulfone compound include β
-Ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. Specific examples of the sulfone compound include phenacylphenyl sulfone,
Mesityl phenacyl sulfone, bis (phenylsulfonyl) methane, 4-trisphenacyl sulfone and the like can be mentioned. Sulfonic acid ester compound: Examples of the sulfonic acid ester compound include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Specific examples of the sulfonic acid ester compound include benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, pyrogallol methanesulfonic acid triester, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, α-methylol benzoin tosylate, α -Methylolbenzoinoctanesulfonate, α-methylolbenzointrifluoromethanesulfonate, α-methylolbenzoindodecylsulfonate and the like. Sulfonimide compound: As the sulfonimide compound, for example, the following formula (6)

[0052]

Embedded image

[In the formula (6), X is an alkylene group,
Represents a divalent group such as an arylene group or an alkoxylene group,
R ⁷ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, and a halogen-substituted aryl group. ] Can be mentioned. Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, and N- (trifluoromethylsulfonyl) Oxy) naphthylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(Trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (10-campanylsulfonyloxy) succinimide, N- (10-campanyl Sulfonyloxy) phthalimide, N- (10-campanylsulfonyloxy) diphenylmaleimide, N-
(10-campanylsulfonyloxy) naphthylimide, N- (10-campanylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-campanyl Sulfonyloxy) -7-oxabicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (10-
Camphanylsulfonyloxy) naphthylimide, N-
(10-Camphanylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-
Dicarboximide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N
-(4-methylphenylsulfonyloxy) naphthylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methyl Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.
1] Heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N-
(2-trifluoromethylphenylsulfonyloxy)
Diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthylimide, N- (2
-Trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2. 2.
1] hept-5-ene-2,3-dicarboximide,
N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (4-
Fluorophenylsulfonyloxy) phthalimide, N
-(4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) naphthylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.1.1] hept-5
-Ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.1.1] hept-5-ene-2,3-dicarboximide, N- ( 4-fluorophenylsulfonyloxy) bicyclo [2.1.1] heptane-5,6-oxy-2,3-dicarboximide and the like. Diazomethane compound: As the diazomethane compound, for example, the following formula (7)

[0054]

Embedded image

[In the formula (7), R ⁸ and R ⁹ each independently represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group and a halogen-substituted aryl group. ] Can be mentioned. Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, and methylsulfonyl-4-methylphenylsulfonyldiazomethane , Cyclohexylsulfonyl-1,1-dimethylethylsulfonyldiazomethane,
Bis (1,1-dimethylethylsulfonyl) diazomethane and the like can be mentioned.

Among the above-mentioned acid generators (D), onium salt compounds, sulfonic acid ester compounds, sulfonimide compounds and diazomethane compounds are preferred, and bis (t-butylphenyl) iodonium 10-camphorsulfonate, triphenylsulfonium trifluorofluoride is particularly preferred. Romethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, pyrogallol methanesulfonic acid triester, α-methylolbenzoin tosylate, α-methylolbenzoinoctanesulfonate, α-methylolbenzointrifluoromethanesulfonate, α-methylolbenzoindodecylsulfonate, N- (10-camphanylsulfonyloxy)
Naphthylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (10-campanylsulfonyloxy) bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, bis (cyclohexylsulfonyl) diazomethane and the like are preferred.

In the present invention, the acid generator (D) can be used alone or in combination of two or more. The amount of the acid generator (D) used is preferably 0.1% by weight per 100 parts by weight of the total of the resin (A), the resin (B) and the resin (C).
It is 1 to 20 parts by weight, more preferably 1 to 10 parts by weight. In this case, if the amount of the acid generator (D) used is less than 0.1 part by weight, the sensitivity and resolution as a resist tend to decrease, while if it exceeds 20 parts by weight, the coating properties and heat resistance of the resist will increase. Tends to decrease.

Other Ingredients The radiation-sensitive resin composition of the present invention may optionally contain various additives such as an acid diffusion controller, a surfactant and a sensitizer. The acid diffusion controller, the purpose of controlling the diffusion phenomenon in the resist film of the acid generated from the radiation-sensitive acid forming agent by exposure, to suppress undesired chemical reaction in the unexposed area, the resin composition It is a component to be blended in. By using such an acid diffusion controlling agent, it is possible to further improve the dimensional fidelity with respect to the pattern shape and the mask dimension. As the acid diffusion controller, for example, a nitrogen compound which can maintain basicity even after exposure or heating in a resist pattern forming step is preferable. Specific examples of such nitrogen compounds include ammonia, trimethylamine, triethylamine, and tri-amine.
n-propylamine, tri-n-butylamine, tri-
n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-dodecylamine, dimethyl n-dodecylamine, dicyclohexylmethylamine, aniline , N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 1-naphthylamine, 2-naphthylamine, diphenylamine, ethylenediamine, tetramethylenediamine, hexa Methylenediamine, pyrrolidone, piperidine, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, thiabendazole, pyridine,
2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, −
Benzylpyridine, 3-benzylpyridine, 4-benzylpyridine, nicotinamide, dibenzoylthiamine, ribofuramine tetrabutyrate, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether,
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 ″ -hydroxy Phenyl) propane, 1,4-bis [1-
(4′-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4′-aminophenyl) -1
-Methylethyl] benzene and the like. Among these acid diffusion controlling agents, particularly, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-dodecyl Amine, dimethyl n-dodecylamine, dicyclohexylmethylamine, benzimidazole, 2-phenylbenzimidazole, 2-
Preferred are phenylpyridine, 4-phenylpyridine, 2-benzylpyridine, 4-benzylpyridine, nicotinamide, 4,4′-diaminodiphenylether and the like. The acid diffusion controllers can be used alone or in combination of two or more. The amount of the acid diffusion controller is
It changes according to the kind, the kind of the acid generator (D), etc.,
Usually, 1 part by weight per 100 parts by weight of all resin components in the resin composition.
0 parts by weight or less, preferably 5 parts by weight or less. In this case, if the amount of the acid diffusion controller exceeds 10 parts by weight, the sensitivity and developability as a resist tend to decrease.

The surfactant has an effect of improving the coating property, striation, developability, etc. of the radiation-sensitive resin composition. Such surfactants include anionic,
Any of a cationic type, a nonionic type and an amphoteric type can be used, but a preferred surfactant is a nonionic type surfactant. Examples of nonionic surfactants include:
In addition to polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, and the like, KP (manufactured by Shin-Etsu Chemical), Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo), Each series such as F-Top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, and Surflon (manufactured by Asahi Glass) can be mentioned. These surfactants can be used alone or in combination of two or more. The amount of surfactant is
As an active ingredient of a surfactant, it is usually 2 parts by weight or less per 100 parts by weight of all resin components in the resin composition. The sensitizer absorbs radiation energy and transmits the energy to the acid generator (D), thereby increasing the amount of acid generated. Has the effect of improving the sensitivity of Preferred sensitizers are acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. These sensitizers can be used alone or in combination of two or more. The compounding amount of the sensitizer is usually 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of all resin components in the resin composition. 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 reduced. it can. Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improver, and the like, specifically, 4-hydroxy-4′-methylchalcone.

Composition Solution The positive-type radiation-sensitive resin composition of the present invention is dissolved in a solvent such that the solid content concentration becomes, for example, 5 to 50% by weight. It is prepared as a composition solution by filtering through a filter. Examples of the solvent include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, lactones, (halogenated) hydrocarbons, and the like. Are ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, acetates, hydroxyacetate , Alkoxyacetates, propionates, lactates, 2-hydroxy-2-methylpropionates, 3-alkoxypropionates, Esters, ketones acyclic or cyclic, acetoacetic esters, pyruvic acid esters, N, N-dialkyl formamides,
Examples thereof include N, N-dialkylacetamides, N-alkylpyrrolidones, γ-lactones, (halogenated) aliphatic hydrocarbons, and (halogenated) aromatic hydrocarbons.

Specific examples of these solvents include 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, and diethylene glycol di-ether. 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 acetate, propylene glycol monoethyl ether acetate, propylene glycol Mono-n-propyl ester Ether acetate, ethyl acetate, n- propyl acetate, isopropenyl acetate n- butyl,
3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl hydroxyacetate, ethyl ethoxyacetate, isopropenyl propionate, 3-methyl-3-methoxybutylpropionate, ethyl lactate,
Ethyl 2-hydroxy-2-methylpropionate, 3-
Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl butyrate, methyl ethyl ketone, cyclohexanone , 2-heptanone, 3-heptanone, 4-heptanone, methyl acetoacetate, ethyl acetoacetate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, toluene, xylene and the like.
Among the above solvents, propylene glycol monoalkyl ether acetates, lactic acid esters, 3-alkoxypropionic acid esters and the like are preferable. The solvents may be used alone or in combination of two or more.

The solvent may further include benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, if necessary.
1-nonanol, benzyl alcohol, benzyl acetate,
One or more high-boiling solvents such as ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate can also be added.

Formation of Resist Pattern The radiation-sensitive resin composition of the present invention contains a resin component having a specific acid-dissociable group in the repeating unit (2) or the repeating unit (3). The acid dissociable group is dissociated by the action of the acid generated from (D) to form a carboxyl group or a phenolic hydroxyl group, whereby the resin component becomes alkali-soluble, thereby forming a positive resist pattern. Things. When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution prepared as described above, by means of spin coating, casting coating, roll coating, for example,
After coating on a substrate such as a silicon wafer or a wafer coated with aluminum to form a resist film, heat treatment (hereinafter, referred to as “PB”) is performed, and then the resist is applied through a predetermined mask pattern. Expose the coating. The radiation that can be used in this case is the emission line spectrum of a mercury lamp (wavelength 254 nm), Kr
Far ultraviolet rays such as F excimer laser (wavelength 248 nm) and ArF excimer laser (wavelength 193 nm) are preferable, but depending on the type of acid generator (D), charged particle beam such as electron beam, X-ray such as synchrotron radiation, etc. Can also be used. Exposure conditions such as radiation dose are appropriately selected according to the composition of the resin composition, the type of additive, and the like. After the exposure, a heat treatment (hereinafter, referred to as “PEB”) is preferably performed in order to improve the apparent sensitivity of the resist. The heating conditions are the composition of the resin composition,
Although it varies depending on the type of the additive, it is usually 30 to 200.
° C, preferably 50 to 150 ° C. Thereafter, a predetermined resist pattern is formed by developing with an alkali developing solution. Examples of the alkali developer include alkali metal hydroxide, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, and 1,8.
-Diazabicyclo [5.4.0] -7-undecene,
One or more alkaline compounds such as 1,5-diazabicyclo [4.3.0] -5-nonene are usually dissolved in a concentration of 1 to 10% by weight, preferably 2 to 5% by weight. An aqueous solution is used. Particularly preferred alkaline developers are aqueous solutions of tetraalkylammonium hydroxides. Further, for example, a suitable amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the developer composed of the alkaline aqueous solution. When a developer composed of an alkaline aqueous solution is used, washing is generally performed after development.

[0064]

Embodiments of the present invention will now be described more specifically with reference to the following examples. However, the present invention is not limited to these embodiments.

Examples 1 to 20 and Comparative Examples 1 and 2 After mixing the components shown in Table 1 or Table 2 (parts based on weight) to form a uniform solution, Teflon having a pore diameter of 0.2 μm The composition solution was prepared by filtration with a membrane filter made of. Next, each composition solution was spin-coated on a silicon wafer, and then subjected to PB at the temperature and time shown in Table 3 or Table 4 to form a 1.0 μm-thick resist film. This resist film is coated with Nikon Corporation K
rF excimer laser irradiation device (trade name: NSR-200
5 EX8A), and exposure was performed with a KrF excimer laser (wavelength: 248 nm) by changing the exposure amount through a mask pattern. In some examples, electron beams were exposed using a simple electron beam direct writing apparatus (50 KeV). After the exposure, PEB was carried out at the temperature and time shown in Table 3 or Table 4. After that, development was carried out at 23 ° C. for 60 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution. After washing for 2 seconds and drying, a positive resist pattern was formed. Table 5 shows the evaluation results of the examples and the comparative examples.

Here, each resist was evaluated in the following manner. After exposure by changing the exposure amount in the resist film formed on a sensitivity silicon wafer is performed immediately post-exposure bake, and then After alkali development, washing with water and drying, when forming a resist pattern line width 0. 25 μm line
The exposure amount that forms the AND space pattern (1L1S) with a line width of 1: 1 was defined as the optimal exposure amount, and the optimal exposure amount was defined as the sensitivity. Resolution The minimum dimension (μm) of the resist pattern that was resolved when exposed at the optimum exposure amount was defined as the resolution. 1L of 0.25μm line width formed on a patterned silicon wafer
The dimension La of the lower side and the dimension Lb of the upper side of the square cross section of 1S are measured using a scanning electron microscope to satisfy 0.85 ≦ Lb / La ≦ 1 and the pattern is clogged near the substrate. A pattern having no eaves in the upper layer of the pattern was determined to have a pattern shape of “good”, and a pattern not meeting at least one of these conditions was determined to be “improper”.

Each component used in each Example and Comparative Example was
It is as follows. In the resin (A) and below, a monomer corresponding to the repeating unit in which R ² in Formula (2) is a hydrogen atom is referred to as “ADA”, and a monomer corresponding to the repeating unit in Formula (2) in which R ² is a methyl group. The term "MD"
A ", and the monomer represented by the formula (4) is referred to as" AD
B ", and the monomer represented by the formula (5) is referred to as" ADC ". A-1: 4-hydroxystyrene / ADA / tricyclodecanyl acrylate copolymer (copolymer molar ratio = 70/20)
/ 10, Mw = 9,000) A-2: 4-hydroxystyrene / ADA copolymer (copolymer molar ratio = 75/25, Mw = 12,000) A-3: 4-hydroxy-α-methylstyrene / ADA /
Isobornyl acrylate copolymer (copolymerization molar ratio = 50
/ 30/20, Mw = 15,000) A-4: 4-hydroxystyrene / ADA / 4-t-butoxystyrene copolymer (copolymerization molar ratio = 65/25/1)
A-5: 4-hydroxystyrene / ADA / 4-t-butoxycarbonyloxystyrene copolymer (copolymer molar ratio = 60/25/15, Mw = 12,000) A- 6: 4-hydroxystyrene / ADA / styrene / A
DB copolymer (copolymer molar ratio = 60/20/17/3,
A-7: 4-hydroxystyrene / MDA / ADC copolymer (copolymerization molar ratio = 65/26/9, Mw = 45,000)
0)

Resin (B) B-1: Resin in which 34 mol% of hydrogen atoms of phenolic hydroxyl groups in poly (4-hydroxystyrene) have been substituted by 1-ethoxyethyl groups (Mw = 9,000). 2: A resin in which 15 mol% of hydrogen atoms of phenolic hydroxyl groups in poly (4-hydroxystyrene) are substituted with 1-ethoxyethyl groups and 18 mol% are substituted with 1-ethoxypropyl groups (Mw = 10, 000) B-3: a resin in which 25 mol% of hydrogen atoms of phenolic hydroxyl groups in poly (4-hydroxystyrene) are substituted with 1-ethoxyethyl groups and 8 mol% are substituted with t-butoxycarbonyl groups ( (Mw = 10,000) B-4: 23 mol% of hydrogen atoms of phenolic hydroxyl groups in poly (4-hydroxystyrene) are substituted by 1-ethoxyethyl groups, and 10 mol% is t-butyl. Group-substituted resin (Mw = 12,000) B-5: 25 mol% of hydrogen atoms of phenolic hydroxyl group in 4-hydroxystyrene / styrene copolymer (copolymerization molar ratio = 90/10) is 1% Resin substituted with cyclohexyloxyethyl group (Mw = 18,000) B-6: phenolic hydroxyl group in 4-hydroxystyrene / t-butyl acrylate copolymer (copolymerization molar ratio = 90/10) Resin in which 25 mol% of hydrogen atoms have been substituted with 1-ethoxyethyl groups (Mw = 18,000) B-7: Poly (4-hydroxystyrene) (Mw = 5.0)
24 mol% of hydrogen atoms of phenolic hydroxyl groups in (00)
Is partially substituted with a 1-ethoxyethyl group and has a hexamer with a crosslinking group having a diethylene glycol skeleton (Mw = 30,000). This resin is a poly (4-hydroxystyrene) (Mw =
5,000) in the presence of pyridinium p-toluenesulfonate in the presence of ethyl vinyl ether and diethylene glycol divinyl ether.

Resin (C) 30% by mole of hydrogen atoms of phenolic hydroxyl groups in C-1: 4-hydroxystyrene / ADA copolymer (copolymerization molar ratio = 90/10) were substituted with 1-ethoxyethyl groups. (Mw = 9,000) C-2: 45 mol% of the hydrogen atoms of the phenolic hydroxyl group in the 4-hydroxystyrene / MDA / ADC copolymer (copolymerization molar ratio = 90/6/4) Resin substituted with 1-ethoxypropyl group (Mw = 30,000)

Acid generator (D) D-1: triphenylsulfonium nonafluoro-n-
Butanesulfonate D-2: bis (4-t-butylphenyl) iodonium 1
0 camphorsulfonate D-3: N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide D-4: bis (cyclohexyl sulfonyl) diazomethane Other As a component alkali solubility control agent, the following formula (8)

[0070]

Embedded image

Compound (α-1) represented by the following formula (9):

[0072]

Embedded image

Using the compound (α-2) represented by the following formula, dimethyl-n-dodecylamine (β-1)
, Tri-n-octylamine (β-2), benzimidazole (β-3) or 2-benzylpyridine (β-4), and as a solvent, ethyl lactate (γ-1), propylene glycol monomethyl ether acetate ( γ-2) or 2-heptanone (γ-3) was used.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

The radiation-sensitive resin composition of the present invention has high sensitivity (low exposure energy) to various types of radiation, particularly to deep ultraviolet rays represented by KRF excimer laser, and has excellent resolution. Performance and pattern shape can be provided. Therefore, the radiation-sensitive resin composition of the present invention is extremely useful, in particular, as a resist for manufacturing semiconductor devices, which is expected to be further miniaturized in the future.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Yukio Nishimura 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Shinichiro Iwanaga 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR F term (reference) 2H025 AA01 AA02 AA03 AB16 AC04 AC05 AC06 AC08 AD03 BE00 BE10 CB14 CB16 CB17 CB41 CB45

Claims (3)

[Claims] 1. A resin containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and (D) a radiation-sensitive acid generator. Radiation-sensitive resin composition. 2. A resin having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): (B) a repeating unit represented by the following formula (1): A radiation-sensitive resin composition comprising a resin having a repeating unit represented by the following formula (3) and (D) a radiation-sensitive acid generator. (C) a resin having a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3), and (D)
A radiation-sensitive resin composition comprising a radiation-sensitive acid generator. Embedded image [In the formula (1), R ¹ represents a hydrogen atom or a methyl group. [Chemical formula 2] [In the formula (2), R ² represents a hydrogen atom or a methyl group. [Chemical formula 3] [In the formula (3), R ³ and R ⁴ independently represent a hydrogen atom or a methyl group, R ⁵ represents a linear or branched alkyl group, and R ⁶ represents a linear, branched or Shows a cyclic alkyl group. ]