JP2002006492A - Radiation-sensitive resin composition - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To have practical sensitivity, to be excellent in pattern shape, resolution, depth of focus, residual film property, to have good margin for escape, and to make pattern side wall rough. To provide a radiation-sensitive resin composition having excellent characteristics. SOLUTION: The radiation-sensitive resin composition contains (A) an alkali-soluble resin and / or a resin which is hardly soluble in alkali and becomes alkali-soluble by the action of an acid, and (B) a compound which generates an acid by the action of radiation. Wherein the repeating unit of the resin constituting the component (A) contains a resin having a repeating unit represented by the following general formula (1), and all of the repeating units of the formula (1) are (A) A radiation-sensitive resin composition, wherein the proportion of the repeating unit in the component resin is 25% or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radiation-sensitive resin composition. More specifically, the present invention relates to a resist composition for producing an ultra LSI, which contains a specific ratio of a repeating unit having a structure of an alkyl-substituted malonic acid derivative. The radiation-sensitive resin composition of the present invention is excellent in pattern shape, resolution, depth of focus, residual film property, and has a good margin for removal, and further has no roughness on the pattern side wall, and is suitable for semiconductor integrated circuit production. is there.

[0002]

2. Description of the Related Art High integration of a semiconductor integrated circuit has progressed at a speed four times as fast as three years as generally known.
As a result, the demand for photolithography technology, which is indispensable for the production of integrated circuits, is increasing year by year.
For example, in the case of a dynamic random access memory (DRAM), a lithography technique of 0.25 μm is required for producing a 256 Mbit DRAM, and about 0.20 μm for a next generation 1 Gbit DRAM. For this reason, the wavelength used for exposing the photoresist has been shortened for the purpose of obtaining a high resolution, and the g-line (436 nm) of the mercury lamp has been changed to the i-line (365 nm).
nm), and at present, KrF excimer laser light (248 nm) in the far ultraviolet region has been used. For future lithography of 0.20 μm or less, a shorter wavelength ArF excimer laser light (1
Lithography using radiation having a wavelength of 93 nm or less and 100 nm or less called vacuum ultraviolet is also being studied.

For exposure at a wavelength shorter than these far ultraviolet rays, the conventional combination of a naphthoquinonediazide compound and a novolak resin has a very low transmittance of the resist film with respect to the exposure wavelength, resulting in low sensitivity. And there was a problem that sufficient resolution could not be obtained. In order to solve this problem, what is generally called a chemically amplified resist has been proposed. For example, in the case of a positive chemically amplified resist, a compound that generates an acid by the action of radiation (hereinafter, referred to as an acid generator) and an acid are used. A resist composition in combination with a decomposable group-containing resin has come to be used. In such a chemically amplified resist,
The acid generated from the acid generator acts as a catalyst to decompose the acid-decomposable group of the acid-decomposable group-containing resin, whereby the exposed portion of the resist film is easily dissolved in the developing solution.
Therefore, it is possible to reduce the amount of the acid generator having a large absorption, and as a result, high sensitivity and high resolution have been achieved.

However, as described above, recently, 0.2 μm
The formation of a very fine pattern of m or less is required, and resist dimensional controllability at a level which has not been a problem in the past has been required. Therefore, there is a need for a resist having good developability of a resist film, which is generally referred to as a margin for omission, and having no roughness on the side wall of the resist. However, none of the resists has satisfactory performance. For example, in order to improve the developability of a resist, Japanese Patent Application Laid-Open Nos.
JP-A No. 8828, JP-A-11-305445, and JP-A-11-310611 disclose that a malonic ester derivative is used as a monomer component of a resin. In the exposed part, two carboxylic acids are generated per one monomer unit,
As a result of improving the dissolution contrast, an effect that a high resolution is obtained is obtained.However, since the acidity of the malonic ester group is high even in the unexposed portion, the developer easily penetrates, and the residual film property of the resist is reduced. Therefore, it has been difficult to achieve both the residual film property and the dropout margin.

In Japanese Patent Application Laid-Open No. 5-61197,
A radiation-sensitive composition comprising a polymer having a repeating unit represented by the following structural formula (6) and a radiation-sensitive acid-forming agent is disclosed. The composition has high sensitivity, high resolution, and dry etching resistance. , Developability (there is no scum or undeveloped residue at the time of development), residual film property (the film does not decrease at the time of development), adhesiveness (the pattern does not peel off at the time of development), heat resistance (the resist pattern does not change due to heat), etc. It is described as having an effect.

[0006]

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(Wherein, R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R ¹¹ and R ¹² each independently represent a hydrogen atom , A substituted methyl group, a substituted ethyl group, a silyl group, a germyl group, or an alkoxycarbonyl group)

Further, in the examples, a polymer in which R ¹⁰ is a hydrogen atom in the formula (6) and the proportion of the repeating unit represented by the formula (6) in the polymer is 67 mol% is described. I have.

[0009]

However, according to the additional test conducted by the present inventors, although it was not expected at all at the time when the pattern forming technology of about 0.5 μm was used, it was found that 0.2 μm was required.
It has been found that, with a fine pattern having a size of about μm, the residual film property is deteriorated, and roughness of the pattern side wall and a defect in a margin for dropout often occur. In particular, in the polymer described in the examples of this publication, in which R ¹⁰ is a hydrogen atom, the residual film properties, the roughness of the pattern side wall and the margin for removal are insufficient, and the polymerized unit represented by the formula (6) When the ratio of the above to all the resin monomers is 30% or more, which is described as a normal range in the publication, it has been found that the sensitivity is extremely low and is not suitable for practical use. An object of the present invention is to provide a radiation-sensitive resin composition which has a good margin for removal, has no pattern side wall roughness, and can form a fine pattern of 0.2 μm or less.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above circumstances, and as a result, have found that a resist composition for manufacturing an VLSI contains a specific proportion of a repeating unit having a specific alkyl-substituted malonic acid derivative structure. By doing so, it is possible to exhibit characteristics that have practical sensitivity, are excellent in pattern shape, resolution, depth of focus, residual film properties, have a good margin for escape, and have no roughness on the pattern side wall. This led to the completion of the present invention.

That is, the gist of the present invention is to provide (A) an alkali-soluble resin and / or a resin which is hardly soluble in alkali and becomes alkali-soluble by the action of an acid, and (B) a compound which generates an acid by the action of radiation. A radiation-sensitive resin composition comprising a resin having a repeating unit represented by the following general formula (1) in a repeating unit of the resin constituting the component (A), and a resin represented by the formula (1): The proportion of the repeating units in the total repeating units in the resin (A) is 25.
% Or less in the radiation-sensitive resin composition.

[0012]

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(Wherein R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
0 represents a substituted or unsubstituted alkyl group; R ² represents an organic group having 1 or more carbon atoms; R ³ and R ⁴ each independently represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, or 2 to 10 carbon atoms Represents a substituted or unsubstituted alkoxycarbonyloxy group. However, R ³ and R ⁴
Is a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms or a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 10 carbon atoms. X represents a divalent organic group having 1 or more carbon atoms)

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Resin Component (A)) In the present invention, the resin component (A) comprises an “alkali-soluble resin” and / or a “resin that is hardly soluble in alkali and becomes alkali-soluble by the action of an acid”. Means that the resist film obtained by applying the radiation-sensitive resin composition to a substrate has sufficient solubility in an alkali developing solution and developing conditions used for pattern formation and is completely eluted, The solubility means that the resist film obtained by applying the radiation-sensitive resin composition to a substrate does not dissolve at all or hardly dissolves in the alkali developing solution and developing conditions used for pattern formation, and the resist film remains only slightly. Say that.

The repeating unit represented by the formula (1) is not particularly limited as long as it has a structure represented by the formula (1), but R ¹ is usually a hydrogen atom or a carbon atom having 1 or more and 10 or less, preferably none. Is a substituted alkyl group, if the carbon number of the alkyl group is large, the hydrophobicity of the resin becomes strong, so that the solubility of the exposed portion of the resist in an alkali developing solution decreases,
Resolution and missing margins tend to decrease. R ¹ is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.
In the formula (1), X is a divalent organic group having 1 or more carbon atoms, and specific examples include groups represented by the following structural formulas (7) to (110).

[0016]

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[0017]

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[0018]

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[0019]

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X is preferably an organic alicyclic hydrocarbon group or an organic group containing an aromatic ring.
The above structural formulas (7) to (24) and (37) to (110)
It is a group of. Particularly preferred is a group represented by the following general formula (2) having good dry etching resistance of the resist film.

[0021]

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(Where Y represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms)

Preferred specific examples of the group represented by (2) include the above structural formulas (11) and (93) to (110). Next, in the formula (1), R ² usually has 1 carbon atom.
The above organic groups, from the viewpoint of the effect that the residual film property of the present invention is good and the escape margin is good, preferably a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group , Sec-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1-
Methylbutyl group, 1-ethylpropyl group, n-hexyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 2-ethylhexyl group,
n-nonyl group, n-decyl group, 1-methylnonyl group, n
-Undecyl group, lauryl group, 1-methylundecyl group, n-tridecyl group, 1-methyldodecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, Cyclopropyl group, cyclopropylmethyl group, cyclobutyl group,
Cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group,
A non-substituted alkyl group having 1 to 20 carbon atoms, such as a 2-norbornyl group, a 1-adamantyl group or a 2-adamantyl group, or an unsubstituted alkyl group, or a group represented by the following formula (3).

[0024]

Embedded image -ZG (3)

(Where Z represents a divalent organic group, G represents a hydroxyl group, a carboxyl group, or a group which is decomposed by the action of an acid to increase the solubility in an aqueous alkali solution)

In the formula (3), specific examples of Z include:
The same groups as X, that is, the groups of the structural formulas (7) to (110) can be mentioned. Z is preferably an alkylene group having 1 or more and 20 or less carbon atoms.
5), (28) to (30), (37) to (39), (4)
4) to (46), (51) to (53), (60) to (6)
6), and groups (83) to (88). In the formula (3), G is a group which is decomposed by the action of a hydroxyl group, a carboxyl group or an acid to increase the solubility in an aqueous alkali solution. The group which is decomposed by the action of an acid to increase the solubility in an alkaline aqueous solution is specifically, for example, a group represented by the following general formula (4).

[0027]

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(Provided that R ⁵ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, which may have a heterocyclic ring, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, one of m and n is 1, and the other is 0 or 1.)

Specific examples of R ⁵ include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl and tert.
-Butyl group, n-pentyl group, tert-amyl group, 2
-Methylbutyl group, 3-methylbutyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, lauryl group, cyclopropyl group, cyclopropylmethyl group , Cyclobutyl, cyclobutylmethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cycloheptyl, 2-norbornyl, 1-adamantyl, 2-
Adamantyl group, 2-methyl-2-adamantyl group, 2
Unsubstituted alkyl groups such as -ethyl-2-adamantyl group; benzyl group, phenethyl group, (1-naphthyl) methyl group, (2-naphthyl) methyl group, (9-anthracene) methyl group, o-nitrobenzyl group A substituted or unsubstituted aralkyl group such as m-nitrobenzyl group, p-nitrobenzyl group, 2,6-dinitrobenzyl group; phenyl group, p-toluyl group, 1-naphthyl group, o-methylphenyl group, m -Methylphenyl group, p-methylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethyl Phenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,
3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, o
A substituted or unsubstituted aryl group such as -nitrophenyl group, m-nitrophenyl group, p-nitrophenyl group; or a substituted alkyl group represented by the following general formula (5)

[0030]

Embedded image (However, R ⁷ and R ⁸ are each independently a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, or a substituted or unsubstituted aryl group having a carbon number of 6 to 10, R ⁶ is the number of carbon atoms Represents 1 to 10 substituted or unsubstituted alkyl groups. And R ⁷ and R ⁸ , or R ⁷ or R ⁸ and R ⁶ may be combined to form a ring having 3 to 10 carbon atoms).

Specific examples of the group represented by the formula (5) include:
Methoxymethyl group, 1-ethoxyethyl group, 1-ethoxypropyl group, 1-methoxypropyl group, 2-methoxypropyl group, 2-ethoxypropyl group, tetrahydrofuranyl group, tetrahydropyranyl group, 1-methoxycyclohexyl group, 1 -Ethoxycyclohexyl groups. Preferred as the substituent G in the formula (3) is a group represented by the formula (4) among the above. In the case where R ⁵ in the general formula (4) is any of these groups, if the number of carbon atoms is large, molecules having an undecomposed group present in the exposed portion are less likely to be eluted in a developing solution during alkali development, and may remain as scum. Therefore, among the groups represented by the formula (4), R ⁵ is preferably a methyl group, an ethyl group, an n-propyl group, an is
o-propyl group, n-butyl group, sec-butyl group, i
so-butyl group, tert-butyl group, n-pentyl group, tert-amyl group, 2-methylbutyl group, 3-methylbutyl group, n-hexyl group, n-heptyl group, n-
Octyl group, 2-ethylhexyl group, n-nonyl group, n
-Decyl group, 1-methylnonyl group, n-undecyl group,
Lauryl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, 2-norbornyl group, 1-adamantyl group, 2-adamantyl group, etc. 1 or more carbon atoms
An unsubstituted alkyl group of 2 or less, and a group represented by the general formula (5). More preferably, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert
A linear or branched unsubstituted alkyl group having 1 to 4 carbon atoms, such as -butyl group, or a methoxymethyl group, 1-
Straight-chain, branched having 1 to 5 carbon atoms, such as an ethoxyethyl group, a 1-ethoxypropyl group, a 1-methoxypropyl group, a 2-methoxypropyl group, a 2-ethoxypropyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group. Alternatively, it is a cyclic alkoxy-substituted alkyl group. When R ⁵ is the above-mentioned preferred group, the rate of decomposition by the acid generated upon exposure is high, and the sensitivity tends to be improved.

In the formula (1), R ³ and R ⁴ may be the same or different and include, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.
-Butyl group, iso-butyl group, tert-butyl group,
n-pentyl group, tert-amyl group, 2-methylbutyl group, 3-methylbutyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-
Nonyl group, n-decyl group, lauryl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, 2-
Norbornyl group, 1-adamantyl group, 2-adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-
Preferably an unsubstituted alkyl group having 1 to 12 carbon atoms such as a 2-adamantyl group; a methoxymethyl group, a 1-ethoxyethyl group, a 1-ethoxypropyl group, a 1-methoxypropyl group, a 2-methoxypropyl group; A substituted alkyl group having 1 to 12 carbon atoms such as a 2-ethoxypropyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a 1-methoxycyclohexyl group, and a 1-ethoxycyclohexyl group; a methoxy group, an ethoxy group, and an n-propyloxy group , Iso-propyloxy group, n-butoxy group, s
ec-butoxy group, iso-butoxy group, tert-butoxy group, n-pentyloxy group, tert-amyloxy group, 2-methylbutoxy group, 3-methylbutoxy group, n-hexyloxy group, n-heptyloxy group, n
-Octyloxy group, 2-ethylhexyloxy group, n
-Nonyloxy group, n-decyloxy group, cyclopropyloxy group, cyclopropylmethoxy group, cyclobutoxy group, cyclobutylmethoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclohexylmethoxy group, cycloheptyloxy group, 2-norbornyl An oxy group, a 1-adamantyloxy group, a 2-adamantyloxy group, a 2-methyl-2-adamantyloxy group, a 2-ethyl-2-adamantyloxy group, etc.
The following unsubstituted alkoxy groups: methoxymethoxy group, 1-
Ethoxyethoxy group, 1-ethoxypropyloxy group,
1-methoxypropyloxy group, 2-methoxypropyloxy group, 2-ethoxypropyloxy group, tetrahydrofuranyloxy group, tetrahydropyranyloxy group,
1-methoxycyclohexyloxy group, 1-ethoxycyclohexyloxy group, substituted alkoxy group having 1 to 12 carbon atoms of tert-butoxycarbonylmethyloxy group; phenyl group, 1-naphthyl group, 2-naphthyl group,
o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl Group, 2,5
-Dimethylphenyl group, 2,6-dimethylphenyl group,
3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, such as a trimethylphenyl group, a 2,4,6-trimethylphenyl group, an o-nitrophenyl group, an m-nitrophenyl group, a p-nitrophenyl group; Group, 1-
Naphthoxy group, 2-naphthoxy group, o-methylphenoxy group, m-methylphenoxy group, p-methylphenoxy group, o-methoxyphenoxy group, m-methoxyphenoxy group, p-methoxyphenoxy group, 2,3-dimethylphenoxy group Group, 2,4-dimethylphenoxy group, 2,5-
Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,5-trimethylphenoxy group,
2,3,6-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, o-nitrophenoxy group, m-
A substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms such as a nitrophenoxy group and a p-nitrophenoxy group; a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propyloxycarbonyloxy group,
iso-propyloxycarbonyloxy group, n-butoxycarbonyloxy group, sec-butoxycarbonyloxy group, iso-butoxycarbonyloxy group, ter
t-butoxycarbonyloxy group, n-pentyloxycarbonyloxy group, tert-amyloxycarbonyloxy group, 2-methylbutoxycarbonyloxy group,
3-methylbutoxycarbonyloxy group, n-hexyloxycarbonyloxy group, n-heptyloxycarbonyloxy group, n-octyloxycarbonyloxy group, 2-ethylhexyloxycarbonyloxy group, n
-Nonyloxycarbonyloxy group, cyclopropyloxycarbonyloxy group, cyclopropylmethoxycarbonyloxy group, cyclobutoxycarbonyloxy group,
C2 to C10 such as cyclobutylmethoxycarbonyloxy, cyclopentyloxycarbonyloxy, cyclohexyloxycarbonyloxy, cyclohexylmethoxycarbonyloxy, cycloheptyloxycarbonyloxy, 2-norbornyloxycarbonyloxy, etc. An unsubstituted alkoxycarbonyloxy group; or a methoxymethoxycarbonyloxy group,
1-ethoxyethoxycarbonyloxy group, 1-ethoxypropyloxycarbonyloxy group, 1-methoxypropyloxycarbonyloxycarbonyloxy group, 2
-Methoxypropyloxycarbonyloxy group, 2-ethoxypropyloxycarbonyloxy group, tetrahydrofuranyloxycarbonyloxy group, tetrahydropyranyloxycarbonyloxy group, 1-methoxycyclohexyloxycarbonyloxy group, 1-ethoxycyclohexyloxycarbonyloxy group, etc. And a substituted alkoxycarbonyloxy group having 2 to 10 carbon atoms.

Where R^ThreeAnd R^FourAt least one of is replaced
Or an unsubstituted alkoxy group, or a substituted or unsubstituted
Must be a substituted alkoxycarbonyloxy group
No. R ^ThreeAnd R^FourAre both an alkyl group, an aryl group, and
When the group is selected from among the reeloxy groups, the formula
The repeating unit represented by (1) is a reaction by the action of an acid.
Development of exposed and unexposed areas of the resist film
The change in solubility in liquid is small, and the resolution is reduced.
You. The exposed and unexposed areas of the resist film
Viewpoint of increasing solubility change and improving resolution
And preferably R^ThreeAnd R^FourAre independent of each other,
It is a xy group or an alkoxycarbonyloxy group. Al
Of the oxy and alkoxycarbonyloxy groups
Particularly preferred is tert, which has a high acid decomposition rate.
-Butoxy group, tert-amyloxy group, 1-adama
Ethyl group, 2-methyl-2-adamantyloxy
Or a tertiary amino group such as a 2-ethyl-2-adamantyloxy group.
Lucoxy group, 1-ethoxyethoxy group, 1-ethoxyp
1 such as propyloxy group, 1-methoxypropyloxy group, etc.
-Alkoxy-substituted alkoxy group, tert-butoxy
Alkoxycarbonyl substitution such as rubonylmethyloxy group
Alkoxy group, tert-butoxycarbonyloxy
Group, tert-amyloxycarbonyloxy group, etc.
Primary alkoxycarbonyloxy group, 1-ethoxyethoxy
Cicarbonyloxy group, 1-ethoxypropyloxyca
Rubonyloxy group, 1-methoxypropyloxycarbo
1-alkoxycarbonyloxy group such as niloxy group
is there.

The resin containing the repeating unit represented by the formula (1) can be obtained by polymerizing the corresponding vinyl monomer. May be copolymerized with a vinyl monomer. However, when a homopolymer or a copolymer with another vinyl monomer and the number of repeating units represented by the formula (1) is more than 25% of the total number of repeating units, the resin is used in combination with another resin. The proportion occupied by the number of repeating units represented by the formula (1) in all the component (A) resins can be set to 25% or less.

The vinyl monomer copolymerized with the vinyl monomer corresponding to the repeating unit represented by the formula (1) includes ethylenically unsaturated monomers such as acrylic acid, vinyl alcohol, hydroxystyrene, styrene, maleic acid and derivatives thereof. One or more compounds containing a saturated double bond can be used. Specific vinyl monomers include styrenes such as styrene and 2-phenylpropylene; maleic anhydrides such as maleic anhydride, maleimide and N-methylmaleimide; o-hydroxystyrene;
m-hydroxystyrene, p-hydroxystyrene, 2
-(O-hydroxyphenyl) propylene, 2- (m-
(Hydroxyphenyl) propylene, 2- (p-hydroxyphenyl) propylene, p-tert-butoxycarbonyloxystyrene, 2- (p-tert-butoxycarbonyloxyphenyl) propylene, p-tert
-Butoxycarbonylmethyloxystyrene, 2- (p
Hydroxystyrenes such as -tert-butoxycarbonylmethyloxyphenyl) propylene, p-1-ethoxyethyloxystyrene and 2- (p-1-ethoxyethyloxyphenyl) propylene; acrylic acid, methacrylic acid, methyl acrylate, acrylic Ethyl acrylate, propyl acrylate, butyl acrylate, 1-ethoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
And acrylic acids such as ethoxyethyl methacrylate.

Of the above, hydroxystyrenes and acrylic acids can be suitably used as the comonomer. Examples of the polymerization method include polymerization in the presence of a known radical polymerization initiator, cationic polymerization initiator, or anionic polymerization initiator. Hydrogenated ones for reducing the absorbance can also be preferably used. Further, for the purpose of controlling the molecular weight distribution of the resin, a resin obtained by removing a low molecular weight component or a high molecular weight component of the resin by a known method such as fractional precipitation by recrystallization after polymerization, fractionation by column chromatography, etc. Is also possible. The preferred weight average molecular weight of the resin is 1,000 to 100,000 in terms of polystyrene by GPC measurement. Below this range, the coatability of the composition is reduced, and above this range, the alkali solubility of the exposed areas is reduced. In particular, in order to achieve the effects of the present invention such that the resolution, the depth of focus, and the margin for omission are good, it is particularly preferable to be 1,500 to 50,0.
00.

The resin component (A) has the formula (1)
It is also possible to use other resins in addition to the resin containing a repeating unit represented by The resin that can be used in combination is not particularly limited as long as it is an alkali-soluble resin generally used in a chemically amplified resist or a resin in which all or a part of the alkali-soluble group of the alkali-soluble resin is protected with an acid-decomposable group. Polyhydroxystyrenes such as novolak resins, homopolymers of hydroxystyrene or copolymers of hydroxystyrene and various vinyl monomers; carboxylic acids containing ethylenically unsaturated double bonds such as acrylic acid and methacrylic acid Or a resin in which all or a part of a phenolic hydroxyl group or a carboxyl group is protected by an acid-decomposable group, such as a copolymer of the above carboxylic acids and hydroxystyrenes or various vinyl monomers. Among these, polymers of one or more monomers selected from hydroxystyrene, acrylic acid, and methacrylic acid; polymers of styrene with at least one monomer of hydroxystyrene, acrylic acid, and methacrylic acid; Alternatively, a resin obtained by protecting all or a part of the hydroxyl group or carboxyl group of these resins with an acid-decomposable group has good compatibility with the resin having a repeating unit represented by the formula (1), and a uniform coating film can be obtained. Therefore, it is preferably used.

As the acid-decomposable group, any acid-decomposable group can be used as long as it is eliminated by an acid generated upon exposure to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxylic acid in the resin. , An ethoxy group,
n-propyloxy group, iso-propyloxy group, n
-Butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group, n-pentyloxy group, t
ert-amyloxy group, 2-methylbutoxy group, 3-
Methylbutoxy group, n-hexoxyoxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group,
Cyclopropyloxy group, cyclopropylmethoxy group,
Cyclobutoxy group, cyclobutylmethoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclohexylmethoxy group, cycloheptyloxy group, 2-norbornyloxy group, 1-adamantyloxy group, 2-adamantyloxy group, 2-methyl- An unsubstituted alkoxy group having 1 to 12 carbon atoms such as a 2-adamantyloxy group and a 2-ethyl-2-adamantyloxy group; a methoxymethoxy group, a 1-methoxyethoxy group, a 1-methoxypropoxy group, and a 1-methoxybutoxy group , 1-ethoxyethoxy group, 1-ethoxypropoxy group, 1-ethoxybutoxy group, 1- (n-butoxy) ethoxy group, 1- (iso
-Butoxy) ethoxy group, 1- (sec-butoxy) ethoxy group, 1- (tert-butoxy) ethoxy group, 1
-(Cyclohexyloxy) ethoxy group, tetrahydrofuranyloxy group, tetrahydropyranyloxy group, 1
-Methoxy-1-methylmethoxy group, 1-methoxy-1
1-alkoxy-substituted alkoxy groups such as -methylethoxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, iso-
Propoxycarbonyloxy group, n-butoxycarbonyloxy group, sec-butoxycarbonyloxy group, i
An alkoxycarbonyloxy group such as a so-butoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and a menthyloxycarbonyloxy group is used. (In the present specification, the acid-decomposable group includes a phenolic hydroxyl group or a carboxylic acid-derived oxygen atom.)

Of the acid-decomposable groups, preferred is tert.
A tertiary alkoxy group having 1 to 12 carbon atoms, such as -butoxy group, tert-amyloxy group, 2-methyl-2-adamantyloxy group, 2-ethyl-2-adamantyloxy group; 1-methoxyethoxy group, 1- Methoxypropoxy group, 1-methoxybutoxy group, 1-ethoxyethoxy group, 1-ethoxypropoxy group, 1-ethoxybutoxy group, 1- (n-butoxy) ethoxy group, 1- (iso
-Butoxy) ethoxy group, 1- (sec-butoxy) ethoxy group, 1- (tert-butoxy) ethoxy group, tetrahydrofuranyloxy group, tetrahydropyranyloxy group, etc. And tertiary alkoxycarbonyloxy groups having 1 to 6 carbon atoms, such as tertiary alkoxy groups and tert-butoxycarbonyloxy groups.

In the resin component (A), the proportion of the repeating unit represented by the formula (1) is 25% or less, usually 0.1 to 25% of the total number of repeating units, preferably
It is 0.5 to 20%, more preferably 1 to 10%.
When the proportion of the repeating unit represented by the formula (1) is smaller than this range, there is a possibility that the side wall is not roughened and the effect of the present invention that a good margin for removal is not sufficiently obtained. Rate tends to decrease, and the pattern shape of the resist tends to deteriorate. If the proportion of the repeating unit represented by the formula (1) is larger than this range, the sensitivity is lowered, and there is a possibility that it will not be practical. When a resin having a repeating unit represented by the formula (1) is used in combination with another resin, the resin component (A)
The mixing ratio of the resin having the repeating unit represented by the formula (1) is usually 5 parts by weight of the resin having the repeating unit represented by the formula (1) per 100 parts by weight of the resin component (A). And preferably at least 10 parts by weight, more preferably at least 15 parts by weight. If the mixing ratio of the resin having the repeating unit represented by the formula (1) is small, there is a possibility that the side wall is not roughened and the effect of the present invention that the removal margin is good cannot be sufficiently obtained.

(Compound (B) that Generates an Acid by the Action of Radiation) The compound (B) that generates an acid by the action of radiation (hereinafter referred to as “radiation-sensitive compound”) used in the present invention includes There is no particular limitation as long as it generates an acid by the radiation used in step (a), and conventionally known ones can be used. Specifically, for example, tris (trichloromethyl) -s-triazine, tris (tribromomethyl) -s-triazine, tris (dibromomethyl) -s-triazine, 2,4-bis (tribromomethyl) -6- Halogen-containing s-triazine derivatives such as methoxyphenyl-s-triazine; halogen-substituted paraffins such as 1,2,3,4-tetrabromobutane, 1,1,2,2-tetrabromoethane, carbon tetrabromide and iodoform Halogen-substituted cycloparaffinic hydrocarbons such as hexabromocyclohexane, hexachlorocyclohexane, hexabromocyclododecane, bis (trichloromethyl) benzene, bis (tribromomethyl)
Halogen-containing benzene derivatives such as benzene, tris (2,
Halogen-containing isocyanurate derivatives such as 3-dibromopropyl) isocyanurate, triphenylsulfonium chloride, triphenylsulfonium methylsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium Sulfonium salts such as phenylsulfonium hexafluoroarsenate and triphenylsulfonium hexafluorophosphonate, diphenyliodonium chloride, diphenyliodonium methylsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium tetrafluoroborate, diphenyl Iodonium salts such as nyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphonate, di (4-tert-butylphenyl) iodonium camphanyl sulfonate; methyl p-toluenesulfonate, ethyl p-toluenesulfonate, p-toluenesulfonic acid Butyl, phenyl p-toluenesulfonate, 1,2,3-tri (p-toluenesulfonyl) benzene, p-toluenesulfonic acid benzoin ester, ethyl methanesulfonate, butyl methanesulfonate, 1,2,3-tri ( Methanesulfonyl) benzene, phenyl methanesulfonate, benzoin methanesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, butyl trifluoromethanesulfonate, Sulfonic acid esters such as 2,2,3-tri (trifluoromethanesulfonyl) benzene, phenyl trifluoromethanesulfonate and benzoin trifluoromethanesulfonate; disulfones such as diphenyldisulfone; bis (cyclohexylsulfonyl) methane, bis (phenylsulfonyl) ) Bismethonylmethanes such as methane; o-nitrobenzyl esters such as o-nitrobenzyl-p-toluenesulfonate; and sulfone hydrazides such as N, N-di (phenylsulfonyl) hydrazide. It is also effective to use tripromomethylphenylsulfone, trichloromethylphenylsulfone, 2,3-dibromosulfolane, or a sulfone compound represented by the following general formula (111) as the radiation-sensitive compound.

[0042]

Embedded image

(Wherein, R ¹³ and R ¹⁴ each independently represent a linear, branched or cyclic alkyl group or an aryl group which may have a substituent. It may further have a substituent, and Q represents a —SO ₂ — group or a —C (＝ O) — group. Specific examples of the sulfone compound represented by the general formula (111) include, for example, cyclohexylcarbonyl (cyclohexylsulfonyl) diazomethane, cyclohexylcarbonyl (ethylsulfonyl) diazomethane, cyclohexylsulfonyl (ethylcarbonyl) diazomethane, iso-propylcarbonyl (iso-propyl) Sulfonyl) diazomethane, te
rt-butylcarbonyl (tert-butylsulfonyl) diazomethane, cyclohexylcarbonyl (2-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl (2-methoxyphenylcarbonyl) diazomethane, cyclohexylcarbonyl (3-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl (3- Methoxyphenylcarbonyl) diazomethane, cyclohexylcarbonyl (4-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl (4-methoxyphenylcarbonyl) diazomethane,
Cyclohexylcarbonyl (2-fluorophenylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, cyclohexylsulfonylethylsulfonyldiazomethane, bis (iso-propylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (sec-butylsulfonyl)
Diazomethane, tert-butylsulfonylmethylsulfonyldiazomethane, tert-butylsulfonylcyclohexylsulfonyldiazomethane, bis (cyclopentylsulfonyl) diazomethane, cyclopentylsulfonyl-tert-butylsulfonyldiazomethane, bis (iso-amylsulfonyl) diazomethane, cyclohexylsulfonyl (2-methoxyphenyl) Sulfonyl)
Diazomethane, cyclohexylsulfonyl (3-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl (4-methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl (2-methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl (3-methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl (4 -Methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl (2-fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl (2-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl (4-
Fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl (4-fluorophenylsulfonyl)
Diazomethane, cyclohexylsulfonyl (4-chlorophenylsulfonyl) diazomethane, cyclopentylsulfonyl (4-chlorophenylsulfonyl) diazomethane, cyclohexylsulfonyl (3-trifluoromethylsulfonyl) diazomethane, cyclopentylsulfonyl (3-trifluoromethylsulfonyl) diazomethane, cyclohexylsulfonyl (4 -Trifluoromethoxysulfonyl) diazomethane, cyclopentylsulfonyl (4-trifluoromethoxysulfonyl) diazomethane, cyclohexylsulfonyl (1,3,5-trimethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl (2,3,4-trimethylphenylsulfonyl) diazomethane, Cyclohexylsulfonyl (1,
3,5-triethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl (2,3,4-triethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl (1,3,5-trimethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl (2
3,4-trimethylphenylsulfonyl) diazomethane, o-toluenesulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, m-toluenesulfonyl (2,4,6-trimethylphenylsulfonyl)
Diazomethane, p-toluenesulfonyl (2,4,6-
Trimethylphenylsulfonyl) diazomethane, 2-methoxyphenylsulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, 3-methoxyphenylsulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, 4-methoxyphenylsulfonyl (2 4,6-trimethylphenylsulfonyl) diazomethane, 2-chlorophenylsulfonyl (2,4,6-
Trimethylphenylsulfonyl) diazomethane, 3-chlorophenylsulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, 4-chlorophenylsulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, 2-fluorophenylsulfonyl (2,4,4) 6-trimethylphenylsulfonyl) diazomethane, 3-fluorophenylsulfonyl (2,4,6
-Trimethylphenylsulfonyl) diazomethane, 4-
Fluorophenylsulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, 3-trifluoromethylsulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, 4-trifluoromethylsulfonyl (2,4,6-trimethylphenyl) Sulfonyl)
Diazomethane, 2,3-dimethylphenylsulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, 2,4-dimethylphenylsulfonyl (2,
4,6-trimethylphenylsulfonyl) diazomethane, 2,5-dimethylphenylsulfonyl (2,4,6
-Trimethylphenylsulfonyl) diazomethane, 2,
6-dimethylphenylsulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, bis- (2
4,6-trimethylphenylsulfonyl) diazomethane, benzenesulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, o-toluenesulfonyl (2,3,6-trimethylphenylsulfonyl) diazomethane, p-toluenesulfonyl (2,3 , 6-Trimethylphenylsulfonyl) diazomethane, 2-methoxyphenylsulfonyl (2,3,6-trimethylphenylsulfonyl) diazomethane, 4-methoxyphenylsulfonyl (2,3,6-trimethylphenylsulfonyl) diazomethane, 4,6-dimethyl -2-hydroxymethylphenylsulfonyl (o-toluenesulfonyl)
Diazomethane, 4,6-dimethyl-2-hydroxymethylphenylsulfonyl (p-toluenesulfonyl) diazomethane, 4,6-dimethyl-2-hydroxymethylphenylsulfonyl (2-methoxyphenylsulfonyl)
Diazomethane, 4,6-dimethyl-2-hydroxymethylphenylsulfonyl (4-methoxyphenylsulfonyl) diazomethane, 4,6-dimethyl-2-hydroxymethylphenylsulfonyl (2-fluorophenylsulfonyl) diazomethane, 4,6-dimethyl- 2-hydroxymethylphenylsulfonyl (4-fluorophenylsulfonyl) diazomethane, 4,6-dimethyl-2-hydroxymethylphenylsulfonyl (2,3-dimethylphenylsulfonyl) diazomethane, 4,6-dimethyl-2-hydroxymethylphenylsulfonyl (2,4-
Dimethylphenylsulfonyl) diazomethane, 4,6-
Dimethyl-2-hydroxymethylphenylsulfonyl (2,5-dimethylphenylsulfonyl) diazomethane, 4,6-dimethyl-2-hydroxymethylphenylsulfonyl (2,6-dimethylphenylsulfonyl) diazomethane, phenylsulfonyl (2-naphthylsulfonyl) Diazomethane, phenylsulfonyl (1-naphthylsulfonyl) diazomethane, 4-methoxyphenylsulfonyl (2-naphthylsulfonyl) diazomethane, 4
-Methoxyphenylsulfonyl (1-naphthylsulfonyl) diazomethane, cyclohexylsulfonyl (2-naphthylsulfonyl) diazomethane, cyclohexylsulfonyl (1-naphthylsulfonyl) diazomethane, 2,
Known ones such as 4,6-trimethylphenylsulfonyl (2-naphthylsulfonyl) diazomethane and 2,4,6-trimethylphenylsulfonyl (1-naphthylsulfonyl) diazomethane are exemplified.

Among these radiation-sensitive compounds, iodonium salts, sulfonium salts and sulfone compounds are preferred. Particularly, iodonium salts, sulfonium salts, and the compound represented by the formula (111) are preferable in terms of sensitivity and resolution, and further, in the compound of the formula (111), Q is -SO
₂ - is preferable compounds are particularly preferred compounds as cyclohexyl sulfonyl (1,3,5-trimethylphenyl) diazomethane, cyclohexylsulfonyl (4-methoxyphenyl) diazomethane, cyclohexylsulfonyl (4-fluorophenyl) diazomethane, benzene Sulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, p-toluenesulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, 4-methoxyphenylsulfonyl (2,4,6-trimethylphenylsulfonyl) diazomethane, bis (2,4,6-trimethylphenylsulfonyl) diazomethane, phenylsulfonyl (2-naphthylsulfonyl) diazomethane, phenylsulfonyl (1- (Futylsulfonyl) diazomethane, 4-methoxyphenylsulfonyl (2-naphthylsulfonyl) diazomethane, 4-methoxyphenylsulfonyl (1-naphthylsulfonyl) diazomethane, cyclohexylsulfonyl (2-naphthylsulfonyl) diazomethane, and cyclohexylsulfonyl (1-naphthylsulfonyl) ) Diazomethane. These radiation-sensitive compounds may be used alone or in combination of two or more.

In the composition of the present invention, the radiation-sensitive compound was added to 100 parts by weight of the resin component (A) of the present invention.
It is used in a proportion of 1 to 30 parts by weight, preferably 0.05 to 20 parts by weight. If the amount of the radiation-sensitive compound is less than this range, the sensitivity is inferior. There is a risk of causing a decline.

(Other components) The radiation-sensitive resin composition of the present invention may further contain additives such as a dissolution inhibitor, an aliphatic alcohol, a nitrogen-containing compound, an organic carboxylic acid, a surfactant and a light absorber. Can be. As the dissolution inhibitor, various compounds known as compounds to be added to this type of chemically amplified positive-type radiation-sensitive composition can be applied,
For example, dissolution inhibitors described in JP-A-8-220740 can be mentioned.

Specific examples of aliphatic alcohols include methanol, ethanol, propanol, butanol,
1,2-butanediol, 1,3-butanediol,
1,4-butanediol, 1,2-pentanediol,
1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, ,
4-cyclohexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11 -Undecanol, 1,2-dodecanediol, 1,12-dodecanediol, 1,2-cyclododecanediol, glycerin-α-monomethyl ether, glycerin-α-monoacetate, glycerin-α-monocaprate, glycerin-α- Monocaprylate, glycerin-α-monolaurate, glycerin-α-monooleate, glycerin-α-monopalmate, 1,2,4-butanetriol, 1,2,3-butanetriol, 2-butyl-2-
Ethyl-1,3-propanediol, 1,2,3-cyclohexanetriol, 1,3,5-cyclohesantriol, 2-deoxy-D-galactose, 6-deoxy-D-galactose, 6-deoxy-L- Galactose, 2-deoxy-D-glucose, D-2-deoxyribose, adonitol, DL-arabinose, DL-
Arabitol, pinacol, 2,2-dimethyl-1,3
-Propanediol, 2-ethyl-1,3-hexanediol and the like. The above aliphatic alcohols may be used alone or as a mixture.

The nitrogen-containing compound is a compound that acts as a base for the acid generated from the radiation-sensitive compound, and prevents the acid generated from the radiation-sensitive compound from diffusing into the unexposed portion. It is preferable to mix them because they have an effect of controlling undesired chemical reactions in the reaction. By blending this nitrogen-containing compound, the pattern shape is improved, the resolution of the resist is improved, and the dimensional fluctuation due to the deposition is suppressed, resulting in extremely excellent process stability. More specifically, see Japanese Patent Application Laid-Open No. 5-12736.
9, JP-A-5-232706, JP-A-7-9267
8, JP-A-9-179300, JP-A-9-2743
12, JP-A-9-325496, JP-A-10-17
No. 7250, JP-A-10-186666, JP-A-10-186666
No. 3,260,015, and the like. Examples thereof include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, and the like. Triethanolamine, tri-iso-propanolamine, 2-diethylaminoethanol,
(Bis-2-hydroxyethyl) aminotrishydroxymethylmethane, ethylenediamine, diethylenetriamine, N, N, N ', N'-tetramethylethylenediamine, piperidine, piperazine, alkylamines such as morpholine, aniline, N, N- Dimethylaniline,
N, N-diethylaniline, o-methylaniline, m-
Arylamines such as methylaniline and p-methylaniline, pyridine, p-aminopyridine, p- (N, N-
Pyridines such as dimethylamino) pyridine can be suitably used.

These nitrogen-containing compounds may be used singly or as a mixture of two or more kinds. The addition amount of the nitrogen-containing compound is 0.0001 parts by weight based on 100 parts by weight of the resin component (A) of the present invention. To 5 parts by weight, preferably 0.001 to 2 parts by weight. When the nitrogen-containing compound is used in an amount in the above range, an effect of preventing a sufficient acid from diffusing into unexposed portions is obtained, and a favorable resist pattern is obtained, which is preferable. However, an excessive amount is not preferable because the sensitivity of the resist is lowered. Organic carboxylic acids are used for the purpose of suppressing a decrease in resist performance due to intrusion of a basic substance from the environment.

Specific examples of the organic carboxylic acid include formic acid,
Acetic acid, propionic acid, n-butyric acid, iso-butyric acid, oxalic acid,
Malonic acid, succinic acid, glutaric acid, adipic acid, acrylic acid, methacrylic acid, maleic acid, aliphatic carboxylic acids such as fumaric acid, ketocarboxylic acids such as pyruvic acid, benzoic acid,
Salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid,
An aromatic carboxylic acid such as phthalic acid, terephthalic acid, or isophthalic acid, or a polymer containing a structural unit of an aromatic carboxylic acid commercially available under the trade name SAX (manufactured by Mitsui Toatsu Chemicals) can be used. The amount of the organic carboxylic acid to be added is 0.0 to 100 parts by weight of the resin component (A) of the present invention.
001 to 10 parts by weight, preferably 0.001 to 5 parts by weight.

Surfactants are added for the purpose of improving the coating properties of the radiation-sensitive resin composition, improving the uniformity of the film thickness during spin coating, and improving the developability of the radiation-sensitive resin composition. Is done. Examples of the surfactant that can be used for such a purpose include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and polyoxyethylene glycol. Laurilate,
Polyoxyethylene glycol distearate, F-Top EF301, EF303, EF352 (manufactured by Tochem Products), Megafac F170, F171, F
172, F173 (manufactured by Dainippon Ink), Florad F
C430, FC431, FC170C (Sumitomo 3M), Asahi Guard AG710, Surflon S-38
2, SC-101, SC-102, SC-103, SC
-104, SC-105, SC-106 (made by Asahi Glass Co., Ltd.), KP341 (made by Shin-Etsu Chemical Co., Ltd.), Polyflow No.
75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo) and the like. These surfactants can be used alone or as a mixture of two or more kinds. Usually, 0.01 to 3 surfactants are used per 100 parts by weight of the resin component (A) of the present invention.
Used in parts by weight.

When an image of a resist is formed on a substrate having a high reflectance, such as aluminum, a light absorbing agent can be added to prevent deterioration of the resist pattern shape due to reflection of exposure light from the substrate. Examples of the light absorbing agent used for such a purpose include naphthoquinonediazide compounds, benzophenones, and compounds containing condensed aromatic rings such as naphthalene and anthracene. These light absorbers can be used alone or in combination of two or more,
Usually, it is used in a ratio of 0.01 to 30 parts by weight of a light absorbing agent to 100 parts by weight of the resin component (A) of the present invention.

The radiation-sensitive resin composition of the present invention is used by dissolving each of the above components in a suitable solvent. The solvent is not particularly limited as long as it has sufficient solubility for each component and other additives of the present invention and gives good coating properties. Ketone solvents such as 2-hexanone and cyclohexanone , Methylcellosolve, ethyl cellosolve, cellosolve solvents such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, butyl acetate, amyl acetate, ethyl butyrate, butyric acid Butyl, methyl lactate, ethyl lactate, ester solvents such as methyl 3-methoxypropionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether Tate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol-based solvents such as dipropylene glycol dimethyl ether, cyclohexanone, methyl amyl ketone, ketone solvents such as 2-heptanone,
Alternatively, a mixed solvent thereof, or a mixture obtained by further adding an aromatic hydrocarbon may be used. The use ratio of the solvent is preferably in the range of 1 to 20 times by weight based on the total amount of solids in the radiation-sensitive resin composition.

When a resist pattern is formed on a semiconductor substrate using the radiation-sensitive resin composition of the present invention, the radiation-sensitive resin composition of the present invention dissolved in a solvent as described above is usually used on a semiconductor substrate. And then subjected to prebaking, pattern transfer by exposure, post-exposure bake (post-exposure bake; PEB), and development steps to be used as a photoresist. Semiconductor substrates are those that are usually used as semiconductor manufacturing substrates,
Examples include a silicon substrate and a gallium arsenide substrate. A spin coater is usually used for coating, and light exposure at 436 nm and 365 nm from a high-pressure mercury lamp and 254 n from a low-pressure mercury lamp are used for exposure.
m, or 157 nm using an excimer laser or the like as a light source,
Light of 193 nm, 222 nm, and 248 nm, X-rays, and electron beams are preferably used. Light at the time of exposure may be broad instead of monochromatic light. Exposure by a super-resolution exposure technique such as a phase shift method, an annular illumination, and a halftone mask is also applicable.

The developer of the radiation-sensitive resin composition of the present invention includes inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, and n-propyl. Primary amines such as amines, diethylamine, di-n
Secondary amines such as -propylamine; tertiary amines such as triethylamine and N, N-diethylmethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide and trimethylhydroxyethylammonium hydroxide; or To which alcohol, a surfactant and the like are added. The radiation-sensitive resin composition of the present invention is useful not only for the production of VLSI, but also for general IC production, mask production, image formation, liquid crystal screen production, color filter production or offset printing. In particular, it is useful for KrF excimer laser exposure and ArF excimer laser exposure.

[0056]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the scope of the invention. In addition, the resin synthesized below, A-1, A-2, A-3, A-4, A-5 and A
Table 2 shows the structure of the -6 repeating unit and the ratio thereof. Synthesis Example 1 (Synthesis of 1-ethoxyethylated polyhydroxystyrene (A-1)) A poly-p-hydroxystyrene (weight 30 g of an average molecular weight of 15,000 and Mw / Mn of 1.12) and 300 mL of 1,3-dioxolane were added and uniformly dissolved. Then, 12.2 g of ethyl vinyl ether was added, and the mixture was heated to 40 ° C. in a water bath. To this, 0.3 g of 36% hydrochloric acid was added, and stirring was continued for 4 hours. After the reaction, 3 mL of 28% aqueous ammonia was added to the reaction solution, followed by stirring for 30 minutes. This reaction solution was dropped into 3 L of pure water, and the resulting precipitate was filtered. Further, the precipitate was dissolved in acetone, and the solution was added dropwise to pure water to cause precipitation, whereby a target polymer was recovered. The precipitated polymer is dried under vacuum and
0.1 g of ethoxyethylated polyvinylphenol was obtained. The obtained polymer was dissolved in deuterated acetone, and the proton NMR spectrum was measured.
7.0 ppm aromatic hydrogen signal and 5.2-5.5.
The area ratio with the acetal methine hydrogen signal in ppm was 12.3: 1. From this result, the acetalization ratio was determined to be 32.5%.

Synthesis Example 2 (Synthesis of 1-ethoxyethylated polyhydroxystyrene (A-2)) Polyhydroxystyrene (weight average molecular weight 15,000)
(0, Mw / Mn 1.12), 30 g of ethyl vinyl ether, and 300 ml of dioxolane were synthesized in the same manner as in Synthesis Example 1 to obtain 29.5 g of 1-ethoxyethylated polyvinylphenol. The obtained polymer was dissolved in deuterated acetone, and the proton NMR spectrum was measured. As a result, a signal of 6.2 to 7.0 ppm of aromatic hydrogen and a signal of 5.2 to 5.5 ppm of acetal methine hydrogen were obtained. The area ratio was 15.0: 1. From this result, the acetalization rate was calculated to be 26.7%.
It became.

Synthesis Example 3 (Synthesis of tert-butoxycarbonylated resin (A-3) of resin A-2) 500 m equipped with a cooling pipe, a nitrogen introduction pipe, a stirrer, and a thermometer
Resin synthesized in Synthesis Example 2 in a four-necked flask L
g and 150 ml of acetone were added and uniformly dissolved, and then 0.1 g of 4-dimethylaminopyridine was further added, followed by heating to 40 ° C. in a water bath. In addition,
1.88 g of tert-butyl dicarbonate was slowly dropped, and reacted at 40 ° C. for 4 hours with stirring. After the reaction, the reaction solution was dropped into 1500 ml of water to precipitate a polymer, and the precipitate was filtered. Further, the precipitate was dissolved in acetone, and the solution was added dropwise to pure water to cause precipitation, whereby a target polymer was recovered. The precipitated polymer was dried under vacuum to obtain 20.2 g of a resin (A-3). The tert-butoxycarbonyloxylation rate was 6.0% from the result of the measurement of the weight loss rate due to thermal decomposition.

Synthesis Example 4 (p-hydroxystyrene and di-
Synthesis of copolymer resin (A-4) with tert-butylmalonylmethylstyrene) 100 m equipped with a cooling pipe, a nitrogen introduction pipe, a stirrer, and a thermometer
P-acetoxystyrene 8.40
g (51.8 mmol), 6.04 g (18.2 mmol) of di-tert-butylmalonylmethylstyrene and 70 ml of toluene were added and stirred to form a uniform solution. Nitrogen was blown into the solution for 1 hour from a nitrogen inlet tube to replace the atmosphere with nitrogen. Next, 0.92 g of azobisisobutyronitrile
(5.6 mmol) and added at 70 ° C. under a nitrogen atmosphere.
Allowed to react for hours. After the reaction, the solution was cooled to room temperature, and n-
It was added dropwise to 700 ml of hexane. The precipitated solid was separated by filtration and dissolved in 70 ml of tetrahydrofuran. This tetrahydrofuran solution was dropped into 700 ml of n-hexane, and the precipitated solid was separated by filtration and dried to obtain 11.23 g of a polymer. Next, a cooling pipe, a stirrer, and a thermometer 10 were provided.
Polymer obtained in 0 mL four-necked flask 10.0
g, 50 ml of methanol and 10 ml of a 28% by weight aqueous ammonia solution were added and reacted at 70 ° C. for 8 hours. After cooling the reaction solution to room temperature, it was added dropwise to 500 ml of water. The aqueous layer was neutralized with 35% by weight hydrochloric acid, and the precipitated solid was separated by filtration. The obtained polymer was dissolved in 20 ml of tetrahydrofuran and added dropwise to 300 ml of water. The precipitated solid is filtered off,
Drying yielded 8.01 g of polymer. When the obtained polymer was dissolved in deuterated acetone and the proton NMR spectrum was measured, it was found to be 6.4 to 7.0 p.
The area ratio between the signal of aromatic hydrogen at pm and the signal of benzylmethylene hydrogen at 3.0 to 3.2 ppm is 8.8.
6: 1. From this result, the monomer ratio of p-hydroxystyrene and di-tert-butylmalonylmethylstyrene in the polymer was determined to be 77.4: 22.6. Gel permeation chromatography (GP
As a result of the measurement of the molecular weight by C), the weight average molecular weight was 11,300 and the number average molecular weight was 6,200 in terms of polystyrene.

Synthesis Example 5 (p-hydroxystyrene and n-
Synthesis of copolymer resin (A-5) with butyl (di-tert-butylmalonyl) methylstyrene 8.40 g of p-acetoxystyrene (51.8 mmol)
l), 7.07 g (18.2 mmol) of n-butyl (di-tert-butylmalonyl) methylstyrene, 70 ml of toluene and 0.92 g of azobisisobutyronitrile
(5.6 mmol) in the same manner as in Synthesis Example 4 except that p-acetoxystyrene and n-butyl (di-ter
7. Copolymer resin of (t-butylmalonyl) methylstyrene
87 g were obtained. Next, p-hydroxystyrene and n-butyl (di-tert-butylmalonylmethyl) were prepared in the same manner as in Synthesis Example 4 except that 7.0 g of the copolymer resin, 40 ml of methanol and 7 ml of a 28% by weight aqueous ammonia solution were used. 5.21 g of a styrene copolymer resin was obtained. The copolymerization ratio of the obtained resin was determined in the same manner as in Synthesis Example 4 by proton NMR.
It was 77.4: 22.6 as determined from the spectrum.
The result of molecular weight measurement by gel permeation chromatography (GPC) was a weight average molecular weight of 11,800 and a number average molecular weight of 6,260 in terms of polystyrene.

Synthesis Example 6 (Synthesis of copolymer resin (A-6) of p-hydroxystyrene and lauryl (di-tert-butylmalonyl) methylstyrene) 6.00 g (37.0 mmol) of p-acetoxystyrene
l), 6.51 g (13.0 mmol) of lauryl (di-tert-butylmalonyl) methylstyrene, 50 ml of toluene and 0.66 g of azobisisobutyronitrile
(4.0 mmol) in the same manner as in Synthesis Example 4, except that p-acetoxystyrene and lauryl (di-tert) were used.
-Butylmalonyl) methylstyrene copolymer resin 5.0
0 g was obtained. Next, p-hydroxystyrene and lauryl (di-tert-butylmalonyl) methylstyrene were prepared in the same manner as in Synthesis Example 4 except that 5.00 g of the copolymer resin, 30 ml of methanol and 5 ml of a 28% by weight aqueous ammonia solution were used. 5.59 g of a copolymer resin was obtained. The copolymerization ratio of the obtained resin was 83.0: 17.0 as determined from the proton NMR spectrum in the same manner as in Synthesis Example 4. As a result of molecular weight measurement by gel permeation chromatography (GPC), the weight average molecular weight was 8250 and the number average molecular weight was 5470 in terms of polystyrene.

(Preparation of Coating Solution for Antireflection Film) 0.1 g of polyvinylpyrrolidone (weight average molecular weight 3000) and 0.4 g of perfluorooctylsulfonic acid were added to deionized water 1
After dissolving in 9.5 g, the solution was filtered through a 0.2 μm membrane filter to obtain an antireflection coating solution (T
1) was prepared. The acidity of the coating solution for antireflection film was 2.0.

Example 1 1.42 g of the resin of A-1, 0.36 g of the resin of A-5, 0.018 g of triphenylsulfonium trifluoromethanesulfonic acid, 0.036 g of bis (cyclohexylsulfonyl) diazomethane, and tri-iso- Dissolve 0.0034 g of propanolamine in 10.2 g of propylene glycol monomethyl ether acetate;
A resist coating solution was prepared by filtration with a m membrane filter. This resist coating solution was spin-coated on a silicon substrate and baked at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 0.72 μm. Next, the resist film was exposed with a Nikon KrF excimer laser stepper (NA = 0.50), baked at 110 ° C. for 90 seconds, and developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds. The obtained resist pattern was evaluated in the following manner.

[Remaining Film Property] The difference between the resist coating film thickness and the film thickness of the unexposed portion after development was evaluated to evaluate (the smaller the number, the better the remaining film property).

[Escape Margin] The line width of the resist was measured with a scanning electron microscope. It was determined by dividing by the exposure amount necessary to develop the substrate (the larger the number, the better).

[Resolution] The minimum line-and-space pattern resolved at the above-mentioned optimum exposure amount was determined by observing with a scanning electron microscope (the smaller the number, the better).

[Depth of Focus] When the focus position of the exposure apparatus is shifted, the width of the focus position at which the 0.24 μm line-and-space mask pattern is resolved at the above optimum exposure amount is observed with a scanning electron microscope. Calculated (the higher the number, the better).

[Roughness of Side Wall] The evaluation was made by observing the roughness of the 0.24 μm line and space resist side wall at the optimum focus position and the optimum exposure amount from the upper surface with a scanning electron microscope.

[Cross-sectional Shape] Evaluation was made by observing a 0.24 μm line-and-space resist cross-sectional shape at an optimum focus position and an optimum exposure amount using a scanning electron microscope. The results are shown in Table 1.

Example 2 1.25 g of the resin of A-1, 0.53 g of the resin of A-5, 0.018 g of triphenylsulfonium trifluoromethanesulfonic acid, 0.036 g of bis (cyclohexylsulfonyl) diazomethane, and tri-iso- Dissolve 0.0034 g of propanolamine in 10.2 g of propylene glycol monomethyl ether acetate;
A resist coating solution was prepared by filtration with a m membrane filter. This resist coating solution was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 1.42 g of the resin of A-1, 0.36 g of the resin of A-4, 0.018 g of triphenylsulfonium trifluoromethanesulfonic acid, 0.036 g of bis (cyclohexylsulfonyl) diazomethane, and tri-iso- Dissolve 0.0034 g of propanolamine in 10.2 g of propylene glycol monomethyl ether acetate;
A resist coating solution was prepared by filtration with a m membrane filter. This resist coating solution was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 1.78 g of the resin of A-1, 0.018 g of triphenylsulfonium trifluoromethanesulfonic acid, 0.036 g of bis (cyclohexylsulfonyl) diazomethane and 0.0034 g of tri-iso-propanolamine were added to propylene glycol monomethyl Ether acetate 1
The resist coating solution was prepared by dissolving in 0.2 g and filtering through a 0.1 μm membrane filter.
This resist coating solution was evaluated in the same manner as in Example 1.
The results are shown in Table 1.

Example 3 1.34 g of resin of A-3, 0.34 g of resin of A-6, 0.035 g of triphenylsulfonium perfluorobutanesulfonic acid, 0.3 g of tri-iso-propanolamine.
0013 g, 0.0009 g of salicylic acid, 0.084 g of 1,4-cyclohexanediol, and glycerin-α
Dissolving 0.034 g of monolaurate in 10.2 g of propylene glycol monomethyl ether acetate,
A resist coating solution was prepared by filtering through a 0.1 μm membrane filter. This resist coating solution was spin-coated on a silicon substrate and baked at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 0.72 μm. Next, a coating solution (T1) for an antireflection film was applied on the resist film and baked at 60 ° C. for 90 seconds. This substrate was treated with a Nikon KrF excimer laser stepper (NA = 0.5
In step 0), exposure was performed using a halftone mask having a light-shielding portion transmittance of 6%, baking was performed at 110 ° C. for 90 seconds, and then 60% with a 2.38 wt% tetramethylammonium hydroxide aqueous solution.
Second development. The obtained resist pattern was evaluated in the following manner.

[Remaining Film Property] The difference between the resist coating film thickness and the film thickness of the unexposed portion after development was evaluated (the smaller the number, the better the remaining film property).

[Escape Margin] The hole diameter of the resist was measured with a scanning electron microscope, and the exposure amount (optimum exposure amount) required for the mask pattern of the 0.26 μm contact hole to be completed according to the mask dimension was determined. It was determined by dividing the amount of exposure necessary for the mask pattern to be developed up to the substrate (larger numbers are better).

[Depth of focus] When the focal position of the exposure apparatus is shifted, the width of the focal position at which the mask pattern of the contact hole is resolved at the above optimum exposure amount is determined by observing with a scanning electron microscope. (Larger numbers are better). The results are shown in Table 1.

Comparative Example 3 1.34 g of resin of A-3, 0.34 g of resin of A-4, 0.035 g of triphenylsulfonium perfluorobutanesulfonic acid, 0.3 g of tri-iso-propanolamine.
0013 g, 0.0009 g of salicylic acid, 0.084 g of 1,4-cyclohexanediol, and glycerin-α
Dissolving 0.034 g of monolaurate in 10.2 g of propylene glycol monomethyl ether acetate,
A resist coating solution was prepared by filtering through a 0.1 μm membrane filter. This resist coating solution was evaluated in the same manner as in Example 3. The results are shown in Table 1.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

According to the present invention, practical sensitivity is obtained,
It is possible to obtain a radiation-sensitive resin composition having excellent pattern shape, resolution, depth of focus, and residual film properties, a good margin for removal, and no pattern sidewall roughness.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 216/14 C08F 216/14 220/02 220/02 220/26 220/26 C08K 5/00 C08K 5 / 00 5/16 5/16 C08L 101/06 C08L 101/06 H01L 21/027 H01L 21/30 502R (71) Applicant 596 156 668 455 Forest Street, Marlborough, MA 01752 U.S.A. A (72) Inventor Noriko Hatohara 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu City F-term (reference) 2K025 AA01 AA02 AA03 AB16 AC04 AC08 AD03 BE00 BE10 BG00 CB14 CB16 CB41 CC20 4J002 BC011 BC041 BC121 BE04 BG011 BG041 BG051 BG061 BG071 BK001 CE001 EB016 EB026 EB046 EB086 EB096 EB116 EB126 EB136 EN027 EN037 EN067 EN107 EU047 EU077 EU186 EU196 EU237 EV216 EV246 EV296 FD310 GP03 HA05 4J100 AB00Q AB07Q AD02P AE32Q AJ02P AJ09P AL03P AL08P AL08Q AM43P AM45P AR09Q AR11Q BA02P BA02Q BA03P BA03Q BA04Q BA05Q BA06P BA06Q BA15Q BA16Q BA20P BA22Q BC02Q BC03Q BC04Q BC07Q BC08Q BC09Q BC43Q BC49Q CA04 DA01 DA04 JA38

Claims (10)

[Claims] 1. A radiation-sensitive resin composition comprising (A) an alkali-soluble resin and / or a resin which is hardly soluble in alkali and becomes alkali-soluble by the action of an acid, and (B) a compound which generates an acid by the action of radiation. Wherein the repeating unit of the resin constituting the component (A) contains a resin having a repeating unit represented by the following general formula (1), and all of the repeating units represented by the formula (1) (A A) a radiation-sensitive resin composition, wherein the proportion of the repeating unit in the component resin is 25% or less; Embedded image (Wherein, R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, R ² represents an organic group having 1 or more carbon atoms, and R ³ and R ⁴ are each independently A substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
Represents a substituted or unsubstituted aryloxy group having from 20 to 20 or a substituted or unsubstituted alkoxycarbonyloxy group having from 2 to 10 carbon atoms. However, at least one of R ³ and R ⁴ is a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms or a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 10 carbon atoms. X represents a divalent organic group having 1 or more carbon atoms) 2. The radiation-sensitive resin composition according to claim 1, wherein X in the formula (1) is an organic alicyclic hydrocarbon group or an organic group containing an aromatic ring. 3. The radiation-sensitive resin composition according to claim 1, wherein X in the formula (1) is a group represented by the general formula (2). Embedded image (Where Y represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms) 4. In the formula (1), R ² has 1 to 20 carbon atoms.
The radiation-sensitive resin composition according to any one of claims 1 to 3, which is a substituted or unsubstituted alkyl group. 5. The radiation-sensitive resin composition according to claim 1, wherein R ² in the formula (1) is a group represented by the following general formula (3). Embedded image wherein Z represents a divalent organic group, and G represents a hydroxyl group, a carboxyl group, or a group which is decomposed by the action of an acid to increase the solubility in an aqueous alkali solution. 6. The formula (3) wherein Z is an unsubstituted alkylene group having 1 to 20 carbon atoms.
3. The radiation-sensitive resin composition according to item 1. 7. In the formula (3), G represents the following general formula (4)
The radiation-sensitive resin composition according to claim 5, which is a group represented by the formula: Embedded image (However, R ⁵ may have a hydrogen atom or a heterocyclic ring,
Represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and one of m and n Is 1 and the other is 0 or 1) 8. In the formula (4), R ⁵ has 1 to 10 carbon atoms.
The radiation-sensitive resin composition according to claim 7, which is a substituted or unsubstituted alkyl group, or a group represented by the following general formula (5). Embedded image (Wherein R ⁷ and R ⁸ are each independently a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, or a substituted or unsubstituted aryl group having a carbon number of 6 to 10, R ⁶ is the number of carbon atoms Represents 1 to 10 substituted or unsubstituted alkyl groups. R ⁷ and R ⁸ , or R ⁷ or R ⁸ and R ⁶ may combine to form a ring having 3 to 10 carbon atoms) 9. The radiation-sensitive resin composition according to claim 1, wherein the compound (B) that generates an acid by the action of radiation is an onium salt or a sulfone compound. 10. The radiation-sensitive resin composition according to claim 1, wherein the radiation-sensitive resin composition further contains a nitrogen-containing basic compound.