JPH11184089A - Radiation sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high photosensitivity and high resolution and to obtain a good pattern shape by incorporating a resin having acid decomposable protective groups and a compd. having acyloxyalkoxy groups. SOLUTION: The radiation sensitive compsn. contains an alkali-soluble resin or a resin having acid decomposable protective groups on at least part of the alkali solubility imparting groups of the resin and a compd. having two or more acyloxyalkoxy groups in one molecule. When the compsn. is applied to a substrate and heated, the alkali-soluble parts of the resin (base resin) which occupies the majority of the compsn. and the acyloxyalkoxy groups (heat crosslinker) cause an exchange reaction. The base resin is crosslinked, the mol.wt. of the resin is increased and the resin is made slightly soluble in an alkali developer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to a radiation-sensitive composition sensitive to radiation, and more particularly to a radiation-sensitive composition suitable as a positive resist for producing a semiconductor integrated circuit.

[0002]

2. Description of the Related Art As the degree of integration of a semiconductor integrated circuit is generally increased four times in three years as generally known, for example, dynamic random access memory (DR)
AM) as an example, full-scale production of a memory having a storage capacity of 64 Mbits has now started. Accordingly, the demand for photolithography technology, which is indispensable for the production of integrated circuits, has been increasing year by year. For example, a 64M DRAM requires a lithography technique of a 0.35 μm rule, and a 256M DRAM having a high degree of integration has been developed.
In a DRAM, a lithography technique of a 0.25 μm rule is required. Along with this, development of a resist that can correspond to each lithography level has been eagerly desired.

Further, for industrial production of integrated circuits, various characteristics as well as resolution have been regarded as important along with miniaturization of processing dimensions. Mass production of integrated circuits requires high throughput of microfabrication processes, high sensitivity with resists, and sufficient performance in image forming processes in a shorter time.

[0004] In today's ultrafine process, the wavelength used for resist exposure is also the i-line of a mercury lamp (365 nm).
From KrF excimer laser light (248 nm), and as a positive resist suitable for such short wavelength exposure, various chemically amplified positive photoresists have been proposed (Japanese Patent Publication No. Hei 2- 27660, JP-A-63
-27829). The chemically amplified resist controls the solubility of a radiation-irradiated portion in a developing solution by a catalytic action of an acid generated by irradiation of radiation (ultraviolet rays, far-ultraviolet rays, X-rays, charged particle beams such as electron beams, etc.). It is a resist and contains a compound whose solubility in an alkali developing solution is increased by an acid catalyzed reaction with an acid generator. Such a chemically amplified positive photoresist is required to be further improved in resolution and rectangularity.

Attempts to increase the solubility difference between unexposed and exposed areas have been made using resist materials containing an alkali-soluble resin, a photoacid generator, and a compound having two or more vinyl ether groups in the molecule (Japanese Patent Application Laid-Open No. 5-100429). , 5-100
428) has been proposed. In this method, after a resist solution is applied, it is thermally crosslinked on a substrate by baking to make it alkali-insoluble, and the crosslinked portion is decomposed with an exposed acid to form an image. However, in this method, since the alkali solubility of the base resin is large, it is necessary to add a large amount of a compound having a vinyl ether group, and scum is likely to be generated during development. However, there is a problem that the resolution deteriorates due to insufficient dissolution contrast.

Further, instead of the alkali-soluble resin, a resin in which an alkali-soluble group of a specific alkali-soluble resin is partially protected with a specific substituent capable of decomposing with an acid, a photoacid generator, and a vinyl ether group in the molecule. A resist material containing one or more compounds has been proposed (Japanese Patent Application Laid-Open No.
-274320). In this method, the resolution is maintained by adding a small amount of a compound having two or more vinyl ether groups in the molecule, but it is difficult to cross-link all of the vinyl ether compounds depending on the process conditions. Since the compound is alkali-insoluble, scum is likely to be generated during development, and a relatively high temperature or a long time is required to perform sufficient crosslinking, which is insufficient for current high throughput process conditions. It turned out to be. Further, Japanese Unexamined Patent Publication No.
In No. 62006, an acidic compound is further added.
When the substituent protecting the alkali-soluble portion is a substituent such as an acetal group which is decomposed by reacting with an acid at room temperature, the storage stability of the resist solution is poor.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel radiation-sensitive composition which solves the above-mentioned problems of the prior art. That is, an object of the present invention is to provide a radiation-sensitive composition having high photosensitivity and high resolution and having a good pattern shape.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by adding a specific compound as a component of the radiation-sensitive composition, the exposed portion and the unexposed portion can be formed under the conventional film forming process conditions. It has been found that the contrast of the exposed portion is improved, and that a good pattern shape can be obtained particularly when used as a photoresist for producing a semiconductor integrated circuit. That is, the gist of the present invention is (a) an alkali-soluble resin or a resin having an acid-decomposable protecting group in at least a part of an alkali-solubility-providing group of the resin;
(B) A radiation-sensitive composition comprising a compound having at least two or more acyloxyalkoxy groups in one molecule. Particularly preferably, the acyloxyalkoxy group has the following general formula (1)

[0009]

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(Wherein, R ^{1 to} R ³ independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group). The heat-sensitive radiation-sensitive composition described above further comprises an acid generator that generates an acid by the action of radiation.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
A feature of the radiation-sensitive composition of the present invention is a compound having at least two or more acyloxyalkoxy groups in one molecule, preferably a group represented by the formula (1) (hereinafter, may be abbreviated as the thermal crosslinking agent). ). The thermal crosslinking agent is added to the radiation-sensitive composition, applied to a substrate, and heated, so that at least the alkali-soluble resin or the alkali-solubility-imparting group of the resin makes up the majority of the components of the radiation-sensitive composition. An alkali-soluble site of a resin partially having an acid-decomposable protecting group (hereinafter, these may be collectively referred to as a base resin) and the thermal crosslinking agent cause an exchange reaction to crosslink between the base resins, The molecular weight of the resin increases, and the resin becomes extremely difficult to dissolve in an alkali developer.
After that, when exposed through a mask, the cross-linking site is decomposed by the acid generated by light, so that the dissolution rate in an alkali developing solution is increased, and it is considered that an image is formed by development. In addition, even when the thermal crosslinking agent is present in a partially unreacted state in the composition, it is decomposed even by the acid generated by exposure,
It is considered that since an alkali-soluble compound is generated, the dissolution rate of the exposed portion is improved, the dissolution contrast is significantly increased, and the resolution and the rectangularity are improved. In a compound having a plurality of vinyl ether groups, since the compound itself is not acid-decomposable, if an unreacted group remains, it does not become alkali-soluble and does not cause scum or increase contrast. it is conceivable that.

The acyl moiety of the acyloxyalkoxy group of the present invention can have a substituent, and the alkoxy moiety can also have a substituent on the alkylene chain. Specific examples of the thermal crosslinking agent used in the present invention include a compound having two or more groups represented by the following general formula (1) in one molecule.

[0013]

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(Wherein, R ^{1 to} R ³ independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group.) ^{As the} alkyl group represented by ¹ , generally a methyl group,
Ethyl group, vinyl group, n-propyl group, iso-propyl group, n-butyl group, allyl group, iso-butyl group, t
A butyl group, a pentyl group, a cyclohexyl group, a norbornyl group, a linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms such as an adamantyl group; examples of the aryl group include a phenyl group and a naphthyl group; p-tolyl group,
m-tolyl group, o-tolyl group, p-butylphenyl group,
m-butylphenyl group, o-butylphenyl group, 2,3
-Dimethylphenyl group, 2,4-dimethylphenyl group,
The 2,4,6-trimethylphenyl group and the like are mentioned, and the alkenyl group is an alkenyl group having 1 to 20 carbon atoms such as an allyl group. When the alkyl group, aryl group or alkenyl group represented by R ^{1 to} R ³ has a substituent, examples of the substituent include a halogen atom, an acyl group, an alkoxy group, an amino group which may have an alkyl group, and a cyano group. Group, an aryl group, and an aryloxy group.

Examples of the substituted alkyl group, aryl group and alkenyl group include halogen-substituted alkyl groups such as chloromethyl group, chloroethyl group, trichloromethyl group and trifluoromethyl group, acetylmethyl group and benzoylmethyl group. Acyl-substituted alkyl group, aryl-substituted alkyl group such as benzyl group, p-methoxyphenyl group, m-methoxyphenyl group, alkoxy-substituted aryl group such as o-methoxyphenyl group, p-aminophenyl group, m-aminophenyl group, o-aminophenyl group, p
An amino-substituted aryl group which may be alkyl-substituted, such as -dimethylaminophenyl group, m-dimethylaminophenyl group, o-dimethylaminophenyl group, p-nitrophenyl group, m-nitrophenyl group, o-nitrophenyl group Nitro-substituted aryl group, p-benzoylphenyl group, m-benzoylphenyl group, acyl-substituted aryl group such as o-benzoylphenyl group, fluorophenyl group,
Examples include a halogen-substituted aryl group such as a chlorophenyl group, a bromophenyl group, and an iodophenyl group, but are not particularly limited thereto.

R ¹ is preferably an optionally substituted alkyl or aryl group having 1 to 20 carbon atoms. R ²
Is preferably a hydrogen atom or an alkyl group which may be substituted, and the alkyl group has 1 to 10 carbon atoms. Examples of the substituent include those similar to the substituents of the alkyl group represented by R ^1. Among them, a hydrogen atom or an unsubstituted alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. R ³ is preferably an alkyl group which may be substituted, and the alkyl group has 1 to 10 carbon atoms. Examples of the substituent include the same substituents as those of the alkyl group represented by R ^1. Is preferably an unsubstituted alkyl group. More preferably, a group of the following formula

[0017]

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(Wherein, R ³¹ and R ³² independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), and among them, a methyl group is particularly preferred. In the thermal crosslinking agent, the linking group to which two or more acyloxyalkoxy groups are bonded is not particularly limited as long as it is a polyvalent linking group for linking the acyloxyalkoxy groups. Preferred thermal crosslinking agents can be represented by the general formula (I) or (II), including the substituent of the general formula (1) and the polyvalent linking group bonded thereto.

[0019]

Embedded image A - [- O- (R- O-) n -] m -CR 2 R 3 -O-CO-R 1 (I) A - [- B- (R-O-) n -] _{^{m -CR 2 R 3 -O-CO}} -R 1 (II)

In the formulas (I) and (II), A is an m-valent alkyl group, an aryl group, a heterocyclic group or a group comprising a combination thereof, and B is -COO-, -NHCOO-
Or -NHCONH-, wherein R represents a linear or branched alkylene group having 1 to 10 carbon atoms, and n represents 0 or 1 to
10 integer, m is an integer of 2 to 6, R ¹ to R ³ have the same meanings as R ¹ to R ³ in the general formula (1). More preferably, in the general formula (I) or (II), A is

[0021]

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B is -CONH-, R is -CH ₂ CH _2- , n is 1-5,
And m is 2 or 3. The compound represented by the general formula (I) or (II) is, for example, a compound represented by the general formula (II)
A compound represented by the formula (I) or (IV) and a compound represented by the general formula (V):
Can be synthesized by reaction with the compound represented by

[0023]

Embedded image A - [- O- (R- O-) n -] m -CQ 1 = CQ 2 Q 3 (III) A - [- B- (R-O-) n -] m -CQ 1 = CQ ² Q ³ (IV) R ¹ -COOH (V)

(Where Q ^{1 to} Q ³ are a hydrogen atom or an alkyl group, and A, B, R, m and n are the same as A, B, R, m and n in the general formulas (I) and (II)) have the same meanings, R ¹ has the same meaning as R ¹ in the general formula (1).) the reaction conditions, such as an organic solvent, or in the absence of solvent, compound (V) (III) or (IV ), An equivalent amount or (V) is added in excess, and a small amount of an acid catalyst such as a Lewis acid or a protonic acid may be added to the reaction system.
It can be synthesized by reacting at −20 ° C. to 120 ° C. for 5 minutes to 10 hours.

Compounds corresponding to (III) and (IV) can be synthesized according to the method described in JP-A-5-100429. Specific compounds of the thermal crosslinking agent include, but are not limited to, compounds represented by formulas (a-1) to (a-51). However, in the formulas (a-1) to (a-51), R ¹¹ represents a methyl, ethyl or t-butyl group, R ²¹ represents a hydrogen atom or a methyl group, and R ³¹ represents a methyl group.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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The thermal crosslinking agent used in the present invention may be used alone or in combination of two or more. The addition amount of the thermal crosslinking agent is usually preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the base resin. If the amount is less than 0.5 part, the cross-linking is not sufficiently formed, and the effect of the addition may not be sufficiently obtained. May not proceed sufficiently, and the resolution of the resist material may decrease.

The alkali-soluble resin used in the present invention or the resin having an acid-decomposable protecting group in at least a part of the alkali-solubility-imparting group of the alkali-soluble resin becomes alkali-soluble in an exposed portion during development and is eluted in an alkali developer. Any alkali-soluble resin can be used as long as it has a uniform coating film forming ability. Examples of the alkali-soluble resin include novolak resin, polyacrylic acid, polyvinyl alcohol, polyvinyl phenol, polyvinyl benzoic acid, and derivatives thereof. Of these, a novolak resin, polyvinyl phenol or a derivative thereof is particularly preferred. For example, a resin obtained by polymerization of hydroxystyrene alone or copolymerization of hydroxystyrene and various vinyl monomers is exemplified. As a vinyl monomer copolymerized with hydroxystyrene, acrylic acid, methacrylic acid, vinyl alcohol, or derivatives thereof are used.

Novolak resins include phenol, o
-Cresol, m-cresol, p-cresol, 3-
Phenols which may be substituted with an alkyl group or an aryl group such as ethylphenol, 2,5-xylenol, 3,5-xylenol and phenylphenol; 2-methoxyphenol, 4-methoxyphenol and 4-phenoxyphenol Alkoxy or aryloxyphenols; naphthols which may be substituted with an alkyl group such as α-naphthol, β-naphthol, 3-methyl-α-naphthol; 1,3-dihydroxybenzene,
3-dihydroxy-2-methylbenzene, 1,2,3-
A hydroxyaromatic compound such as polyhydroxybenzenes which may be substituted with an alkyl group such as trihydroxybenzene, 1,2,3-trihydroxy-5-methylbenzene, 1,3,5-trihydroxybenzene and formaldehyde; Paraformaldehyde, aliphatic aldehydes such as acetaldehyde, benzaldehyde, aromatic aldehydes such as hydroxybenzaldehyde, and carbonyl compounds such as alkyl ketones such as acetone, for example, hydrochloric acid, sulfuric acid, in the presence of an acid catalyst such as oxalic acid, What was manufactured by heating and carrying out polycondensation is mentioned.

The hydroxy aromatic compound may have a substituent such as a halogen atom, a nitro group and an ester group as long as it does not adversely affect the present invention. If necessary, these resins may be further reduced with hydrogen or the like to reduce the absorbance in the short wavelength region. Examples of the polyvinyl phenol or a derivative thereof preferably include a polyvinyl phenol which may have an alkyl substituent on a main chain or a benzene ring, and specifically, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene. Styrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene,
A resin in which one or more hydroxystyrenes such as 2- (p-hydroxyphenyl) propylene are polymerized in the presence of a radical polymerization initiator, an anionic polymerization initiator or a cationic polymerization initiator is used. Further, a resin which has been hydrogenated to reduce the absorbance of the resin after polymerization may be used.Also, substitution of a halogen atom, a nitro group, an ester group or the like in the aromatic compound monomer may be used unless adversely affecting the present invention. It may have a group. The weight-average molecular weight of the novolak resin, polyvinyl phenol or a derivative thereof is generally in the range of 1,000 to 100,000 in terms of polystyrene (measured by gel permeation chromatography).
Preferably 3,000 to 70,000, more preferably 5,000 to 45,000.

If the molecular weight is smaller than this range, a sufficient coating film as a resist cannot be obtained, and the heat resistance is deteriorated. If the molecular weight is larger than this range, the solubility of the exposed portion in an alkali developing solution decreases, and It is difficult to obtain a pattern. Among the base resins, a resin in which a part of an alkali-solubility-imparting group, in particular, a hydroxyl group is protected by an acid-decomposable protecting group (a protecting group removable by an acid catalyst) is preferable. The protecting group is not particularly limited as long as it is a protecting group which can be eliminated by an acid. Specifically, the following formula (2):
Examples include those having the structures represented by (3) and (4). These protecting groups may be used alone or in combination.

[0042]

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(Wherein R ^{4 to} R ⁸ are independently a hydrogen atom,
It is an alkyl group or an alkoxy group, and R ⁴ and R ⁶ may combine to form a ring. R ⁹ and R ¹⁰ represent an alkyl group. ) The alkyl group or the alkoxy group represented by R ^{4 to} R ⁸ preferably has 1 to 6 carbon atoms, more preferably 1 to 4, and the alkyl group represented by R ⁹ and R ¹⁰ has 1 carbon atom. To 10 are preferred. R ⁴ and R ⁶
Are bonded to form a ring, examples of -R ⁵ -R ⁶ -include an alkylene chain, and -CH ₂ CH ₂ -or -CH
_It is preferably ₂ CH ₂ CH ₂ —.

As a specific example represented by the equation (2),
Ethoxyethyl group, 2-chloroethoxyethyl group, ethoxypropyl group, propoxyethyl group, n-butoxyethyl group, iso-butoxyethyl group, t-butoxyethyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. However, the present invention is not limited to these. An ethoxyethyl group is particularly preferred from the viewpoint of resolution.

As a specific example represented by the equation (3),
Ethoxycarbonyl group, propoxycarbonyl group, t-
Butoxycarbonyl group and the like, but are not limited thereto. Particularly, a t-butoxycarbonyl group is preferable. As a specific example represented by equation (4),
Examples include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, t-butyl, cyclohexyl, norbornyl, adamantyl and the like. Particularly, a t-butyl group is preferred.
The above-mentioned base resins can be used alone or in combination of two or more.

The introduction ratio of the protective group is usually from 0 to 60% from the viewpoint of heat resistance and image forming ability, and more preferably from 10 to 60%, and still more preferably from 20 to 50. . As the base resin of the present invention, a resin having an acid-decomposable protecting group in at least a part of the hydroxyl group of polyvinyl phenol or a derivative thereof, particularly when an excimer laser is used as a light source, is a contrast of the transparency of the resin and the solubility before and after exposure. In particular, the base resin is represented by the following general formula (5).

[0047]

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(Wherein T ¹ , T ² and T ³ represent a group selected from the above formulas (2), (3) and (4), provided that T ¹ , T ² and T ³ are different acid-decomposable compounds) Z ^{1 to} Z ^{8 each} independently represent a hydrogen atom or a methyl group, and w, x, and y are each 0 or a positive number, but w, x, and y are simultaneously 0. And z is a positive number, w, x, y, and z are 0 ≦ w / (w + x + y +
z) ≦ 0.5, 0 ≦ x / (w + x + y + z) ≦ 0.5,
0 ≦ y / (w + x + y + z) ≦ 0.5, 0.4 ≦ z /
Satisfies the relationship of (w + x + y + z) ≦ 0.9. ) Of the resins represented by the above formula (5), more preferably T
¹ is a group of the general formula (2), a resin is a group T ² and T ³ are represented by different and Formula (2) to (4).

These composition ratios are preferably 0.1 ≦ w /
(W + x + y + z) ≦ 0.4, 0 ≦ x / (w + x + y +
z) ≦ 0.2, 0 ≦ y / (w + x + y + z) ≦ 0.2,
0.5 ≦ z / (w + x + y + z) ≦ 0.8. The ratio of w to the whole (w + x + y + z, the same applies hereinafter) is 0.
5, the ratio of x to the whole is 0.5, the ratio of y to the whole is 0.5, the ratio of z to the whole exceeds 0.9, or the ratio of z to the whole is 0.4. Otherwise, the contrast of the alkali dissolution rate may be low and the resolution may be poor. By appropriately selecting the values of w, x, y, and z within the above ranges, it is possible to arbitrarily control the pattern dimension and the pattern shape.

T ¹ , T ² and T ³ are mutually different acid-decomposable protecting groups and represent a group selected from the above formulas (2) to (4), and T ¹ , T ² and T ³ are preferred. The group is
It is the same as the preferable group of the general formulas (2) to (4).
T ¹ , T ² and T ³ are particularly preferably a group selected from an ethoxyethyl group, a t-butoxycarbonyl group and a t-butyl group.

Furthermore, in the base resin of the present invention, when the molecular weight distribution (Mw / Mn) is wide, a low molecular weight or high molecular weight polymer is present, and when a large amount of low molecular weight polymer is present, heat resistance may be reduced. In some cases, when a large amount of high molecular weight polymer is present, some of them are difficult to dissolve in alkali, and may cause tailing after pattern formation. Therefore, as the pattern rule becomes finer, the influence of such molecular weight and molecular weight distribution tends to increase. Therefore, in order to obtain a resist material suitably used for fine pattern dimensions, the molecular weight distribution of the base resin must be as follows. 0 to
A narrow dispersion of 1.5, especially 1.0 to 1.3 is preferred.

Advantageously, the compositions according to the invention comprise an acid generator. The acid generator of the present invention means a substance that generates an acid by the action of radiation such as light or an electron beam used for exposure, and any substance having such an action can be used. Include, for example, tris (trichloromethyl) -s-triazine, tris (tribromomethyl) -s-triazine, tris (dibromomethyl) -s-triazine, 2,4-bis (tribromomethyl) -6-p Halogen-containing s-triazine derivatives such as -methoxyphenyl-s-triazine, 1,2,3,
Halogen-substituted paraffin hydrocarbons such as 4-tetrabromobutane, 1,1,2,2-tetrabromoethane, carbon tetrabromide, iodoform, and halogen-substituted cycloparaffins such as hexabromocyclohexane, hexachlorocyclohexane, and hexabromocyclododecane -Based hydrocarbons, halogen-containing benzene derivatives such as bis (trichloromethyl) benzene, bis (tribromomethyl) benzene, halogen-containing sulfone compounds such as tribromomethylphenylsulfone, trichloromethylphenylsulfone, 2,3-dibromosulfolane, and tris Halogen-containing isocyanurate derivatives such as (2,3-dibromopropyl) isocyanurate, triphenylsulfonium chloride, triphenylsulfonium methanesulfonate, triphenyls Sulfonium salts such as honium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluorophosphonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p- Iodonium salts such as toluenesulfonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroarsenate, and diphenyliodonium hexafluorophosphonate;
Methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, 1,2,3-tri (p-toluenesulfonyloxy) benzene, benzoin p-toluenesulfonate Esters, methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, 1,
2,3-tri (methanesulfonyloxy) benzene, phenyl methanesulfonate, benzoin methanesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, butyl trifluoromethanesulfonate, 1,2,3-tri (trifluoro Sulfonic acid esters such as methanesulfonyloxy) benzene, phenyl trifluoromethanesulfonate and benzoin trifluoromethanesulfonate; o-
O- such as nitrobenzyl-p-toluenesulfonate
Nitrobenzyl esters, sulfone hydrazides such as N, N'-di (phenylsulfonyl) hydrazide, the following general formula (6)

[0053]

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(D is —CH ₂ — or

[0055]

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R ¹¹ and R ¹² each independently represent an optionally substituted alkyl group or an optionally substituted aryl group, and k represents 0 or 1. )
Examples of the compounds represented by the general formula (6) include disulfones such as diphenyldisulfone, and bissulfonylmethanes such as bis (phenylsulfonyl) methane and bis (cyclohexylsulfonyl) methane. , Bis (phenylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane and the like. Among these acid generators, preferably,
A compound represented by the general formula (6), more preferably the following general formula (7)

[0057]

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(Wherein, R ¹¹ and R ¹² each independently represent an alkyl group which may be substituted or an aryl group which may be substituted). Specific examples of the compound represented by the general formula (7) include compounds known from JP-A-9-5990, JP-A-4-219957, JP-A-5-249682, JP-A-4-210960 and cyclohexylsulfonyl- ( o-
(Methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (m-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (p-
(Methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (o-methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (m-
(Methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (p-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (o-
(Fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (m-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (p-
(Fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (o-fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (m-
Fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (p-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (o-
(Chlorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (m-chlorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (p-chlorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (o-chlorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (m-chlorophenylsulfonyl) diazomethane, cyclopentyl Sulfonyl- (p-chlorophenylsulfonyl) diazomethane,
Cyclohexylsulfonyl- (o-trifluoromethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (m-trifluoromethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (p-
(Trifluoromethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (o-trifluoromethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (m-trifluoromethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl-
(P-trifluoromethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (o-trifluoromethoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (m-trifluoromethoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (p-trifluoromethoxyphenylsulfonyl) ) Diazomethane, cyclopentylsulfonyl- (o-
(Trifluoromethoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (m-trifluoromethoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (p-trifluoromethoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2,4,6-trimethylphenylsulfonyl) Diazomethane, cyclohexylsulfonyl- (2,3,4-
Trimethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2,4,6-triethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2,3,4-triethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2,4,6
-Trimethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2,3,4-trimethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2,4,6-triethylphenylsulfonyl)
Diazomethane, cyclopentylsulfonyl- (2,3,
4-triethylphenylsulfonyl) diazomethane, phenylsulfonyl (o-methoxyphenylsulfonyl)
Diazomethane, phenylsulfonyl (m-methoxyphenylsulfonyl) diazomethane, phenylsulfonyl (p-methoxyphenylsulfonyl) diazomethane, bis (o-methoxyphenylsulfonyl) diazomethane,
Bis (m-methoxyphenylsulfonyl) diazomethane, bis (p-methoxyphenylsulfonyl) diazomethane, phenylsulfonyl- (2,4,6-trimethylphenylsulfonyl) diazomethane, phenylsulfonyl- (2,3,4-trimethylphenylsulfonyl) Diazomethane, phenylsulfonyl- (2,4,6-triethylphenylsulfonyl) diazomethane, phenylsulfonyl- (2,3,4-triethylphenylsulfonyl) diazomethane, 2,4-dimethylphenylsulfonyl- (2,4,6-trimethyl Phenylsulfonyl) diazomethane, 2,4-dimethylphenylsulfonyl-
Examples thereof include (2,3,4-trimethylphenylsulfonyl) diazomethane, phenylsulfonyl (o-fluorophenylsulfonyl) diazomethane, phenylsulfonyl (m-fluorophenylsulfonyl) diazomethane, and phenylsulfonyl (p-fluorophenylsulfonyl) diazomethane. These acid generators may be used alone or as a mixture of two or more of them.

The total amount of the acid generator is 0.05 to 20 parts by weight, more preferably 100 parts by weight of the base resin.
Used in 0.1 to 10 parts by weight. If the amount of the acid generator is less than this range, the sensitivity is inferior.If the amount of the acid generator is more than this range, the resist pattern becomes trapezoidal due to a decrease in the solubility of the resist film due to the acid generator, resulting in a decrease in resolution. May cause.

Additives can be added to the radiation-sensitive composition of the present invention to such an extent that the effects of the present invention are not impaired. Examples of the additive include a dissolution inhibitor, a surfactant, a dye, a sensitizer, and a nitrogen-containing compound. The dissolution inhibitor is a compound that controls the solubility of the unexposed portion of the base resin in an alkali developer, and may be a low-molecular compound or a high-molecular resin as long as it has a group capable of leaving by an acid catalysis.
Preferred are compounds in which a hydrogen atom of an acidic functional group such as a phenolic hydroxyl group or a carboxyl group is protected by a group capable of leaving by an acid catalyst. Specifically, Japanese Patent Application Laid-Open No. 9-6200
6, JP-A-9-274320, JP-A-9-28169
7, JP-A-9-278699, JP-A-9-50127,
Compounds described in JP-A-9-236921 are exemplified. Furthermore, the dissolution inhibitors used in the present invention can be used alone or in combination of two or more.

When a dissolution inhibitor is added, it is used in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the base resin. A nitrogen-containing compound is a compound that acts as a base for an acid,
It is effective to prevent the acid generated during the pre-bake or the acid generated from the acid generator during the exposure from moving between the exposure and the post-exposure bake to prevent the resist pattern from changing in dimension. Accordingly, the compound is not particularly limited as long as it can neutralize the acid generated from the acid generator as described above, and examples thereof include an organic amine compound. Specifically, for example, pyrimidine, 2-aminopyrimidine, 4-aminopyrimidine, 5-aminopyrimidine, 2,4-diaminopyrimidine, 2,5-diaminopyrimidine, 4,5-diaminopyrimidine, 4,6-diamino Pyrimidine, 2,4,5-
Triaminopyrimidine, 2,4,6-triaminopyrimidine, 4,5,6-triaminopyrimidine, 2,4
5,6-tetraaminopyrimidine, 2-hydroxypyrimidine, 4-hydroxypyrimidine, 5-hydroxypyrimidine, 2,4-dihydroxypyrimidine, 2,5-
Dihydroxypyrimidine, 4,5-dihydroxypyrimidine, 4,6-dihydroxypyrimidine, 2,4,5-
Trihydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 4,5,6-trihydroxypyrimidine, 2,4,5,6-tetrahydroxypyrimidine, 2
-Amino-4-hydroxypyrimidine, 2-amino-5
-Hydroxypyrimidine, 2-amino-4,5-dihydroxypyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4-amino-2,5-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine,
2-amino-4-methylpyrimidine, 2-amino-5
Methylpyrimidine, 2-amino-4,5-dimethylpyrimidine, 2-amino-4,6-dimethylpyrimidine,
-Amino-2,5-dimethylpyrimidine, 4-amino-
2,6-dimethylpyrimidine, 2-amino-4-methoxypyrimidine, 2-amino-5-methoxypyrimidine,
2-amino-4,5-dimethoxypyrimidine, 2-amino-4,6-dimethoxypyrimidine, 4-amino-2,
5-dimethoxypyrimidine, 4-amino-2,6-dimethoxypyrimidine, 2-hydroxy-4-methylpyrimidine, 2-hydroxy-5-methylpyrimidine, 2-hydroxy-4,5-dimethylpyrimidine, 2-hydroxy-4 , 6-dimethylpyrimidine, 4-hydroxy-
2,5-dimethylpyrimidine, 4-hydroxy-2,6
-Dimethylpyrimidine, 2-hydroxy-4-methoxypyrimidine, 2-hydroxy-4-methoxypyrimidine, 2-hydroxy-5-methoxypyrimidine, 2-hydroxy-4,5-dimethoxypyrimidine, 2-hydroxy-4,6- Dimethoxypyrimidine, 4-hydroxy-2,5-dimethoxypyrimidine, 4-hydroxy-
Pyrimidine compounds such as 2,6-dimethoxypyrimidine, pyridine compounds such as pyridine, methylpyridine, N, N-dimethylaminopyridine and 2,6-dimethylpyridine, diethanolamine, triethanolamine,
Amines substituted with a hydroxyalkyl group having 1 to 4 carbon atoms such as triisopropanolamine, tris (hydroxymethyl) aminomethane, bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane, 2-aminophenol, -Aminophenol, 4
Examples thereof include aminophenols such as aminophenol, and pyridines and amines having a hydroxy group are preferred. The content of the nitrogen-containing compound is preferably from 0.1 to 100 mol%, more preferably from 1 to 50 mol%, based on the content of the acid generator.

The radiation-sensitive composition of the present invention is used by dissolving it in a suitable solvent capable of dissolving the above-mentioned components such as the above-mentioned base resin, acid generator, and the above-mentioned thermal crosslinking agent. Preferred solvents are 2-hexanone, ketone solvents such as cyclohexanone, methyl cellosolve, 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, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, 2-hydroxy-2-methylpropionic acid Ester solvents such as methyl, propylene glycol such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether Solvents, ketone solvents such as cyclohexanone, methyl amyl ketone, and 2-heptanone; Mixed solvents thereof, or the like and further an aromatic hydrocarbon added thereto. The proportion of the solvent used is desirably in the range of 1 to 20 times by weight based on the total amount of the solid content of the photosensitive composition.

When a resist pattern is formed on a semiconductor substrate using the radiation-sensitive composition of the present invention, usually,
The radiation-sensitive composition of the present invention dissolved in a solvent as described above is applied on a semiconductor substrate, and can be used as a photoresist through each step of pre-baking, pattern transfer by exposure, baking after exposure, and development. . The semiconductor substrate is
Usually, it is used as a substrate for semiconductor manufacturing, such as a silicon substrate or a gallium arsenide substrate. still,
If necessary, various known antireflection films can be used on the substrate.

A spin coater is usually used for coating.
For exposure, 254 nm of a low-pressure mercury lamp, 157 nm, 193 nm, 222 nm using an excimer laser or the like as a light source.
Light of 248 nm or an electron beam is preferably used, and it is particularly advantageous to use an excimer laser as a light source. Light at the time of exposure may be broad instead of monochromatic light. Exposure by a phase shift method is also applicable.

The developer of the radiation-sensitive composition of the present invention includes:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate, aqueous ammonia, primary amines such as ethylamine and n-propylamine, 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; To which alcohol, a surfactant and the like are added. The radiation-sensitive 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 lithographic printing. In particular, it is useful for producing a semiconductor integrated circuit.

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Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the examples unless it exceeds the gist thereof. Reference Example 1 Synthesis of 1-ethoxyethylated polyvinylphenol Polyvinylphenol (weight average molecular weight 1720) was placed in a 1 L four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermometer.
0) After adding and dissolving 100 g and 500 mL of tetrahydrofuran, 36.0 g of ethyl vinyl ether was added and stirred for a while to form a uniform solution. 35%
0.5 g of hydrochloric acid was added, the mixture was heated to 40 ° C. by a water bath, and stirring was continued for 2 hours. Thereafter, 5 mL of 28% aqueous ammonia was added to the reaction solution, followed by stirring for 30 minutes. This reaction solution was dropped into 9 L of pure water, and the resulting precipitate was collected by filtration. Further, the precipitate was dissolved in acetone, and the solution was dropped into pure water to cause precipitation, thereby recovering a target resin.
The collected resin was dried under vacuum to obtain 100 g of 1-ethoxyethylated polyvinylphenol. The obtained resin was dissolved in deuterated acetone, and a proton NMR spectrum was measured. A signal of an aromatic hydrogen having a δ value of 6.2 to 7.0 and an acetal methine hydrogen having a δ value of 5.2 to 5.5 were obtained. When the acetalization ratio was determined from the area ratio with the signal, it was 36.0.
%.

Synthesis Example 1 [Compound (a)] 6.01 g of acetic acid was dissolved in 10.1 g of triethylene glycol divinyl ether, and 3 drops of a 1% sulfuric acid-tetrahydrofuran solution were added, followed by stirring for 3 hours. Thereafter, 10 ml of a 5% aqueous sodium hydrogen carbonate solution was added for neutralization, and the mixture was separated. Calcium carbonate was added to the organic layer, further dried over anhydrous sodium sulfate, and further dried under vacuum. Product
Table 1 shows ¹ H-NMR.

Synthesis Example 2 [Compound (b)] The compound was synthesized in the same manner as in Synthesis Example 1. However, instead of triethylene glycol divinyl ether, 12.32 g of tetraethylene glycol divinyl ether was used. Table 1 shows ¹ H-NMR of the product.

Synthesis Example 3 [Compound (c)] The compound was synthesized in the same manner as in Synthesis Example 1. However, instead of triethylene glycol divinyl ether, 7.21 g of cyclohexane dimethanol divinyl ether was used. Table 1 shows ¹ H-NMR of the compound (c).

Synthesis Example 4 [Compound (d)] The compound was synthesized in the same manner as in Synthesis Example 1. However, 10.2 g of pivalic acid was used instead of acetic acid. Compound (d) ¹
The H-NMR is shown in Table 1.

Synthesis Example 5 [Compound (e)] 9.73 g of bisphenol A was added to dimethyl sulfoxide 7
The solution was dissolved in 5 ml, 23.5 g of NaOH pellets were added to the solution, and the mixture was stirred at 75 ° C. for 3 hours. Then add 2 to this solution
-39.8 ml of chloroethyl vinyl ether are added dropwise,
The mixture was further stirred at 80 ° C. for 5 hours. After cooling, the mixture was poured into 1 liter of water, extracted with ether, and dried over anhydrous sodium sulfate. The low-boiling substances were removed with an evaporator, and bisphenol A divinyl ether was obtained by column chromatography. Next, 17.2 g of the above synthetic compound was used in place of triethylene glycol divinyl ether, and synthesized in the same manner as in Synthesis Example 1. ¹ H-NM of compound (e)
R is shown in Table 1.

Synthesis Example 6 [Compound (f)] A compound was synthesized in the same manner as in Synthesis Example 1. However, instead of triethylene glycol divinyl ether, 7.08 g of trimethylolpropane trivinyl ether was used.
Table 1 shows ¹ H-NMR of the compound (f). The structures of the compounds (a) to (f) and the comparative compound are summarized below.

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Embedded image

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[Table 1]

Example 1 1.00 g of the resin synthesized in Reference Example 1 was used as an acid generator.
0.02 g of cyclohexylsulfonyl p-methoxyphenylsulfonyldiazomethane, 15 mol% of triisopropanolamine of an acid generator and 5.20 g of propylene glycol monomethyl ether acetate were mixed,
Further, 0.02 g of the compound (a) synthesized in Synthesis Example 1 was added to obtain a resist photosensitive solution. This photosensitive solution is coated on a silicon substrate with an antireflection film (manufactured by Brewer Science).
DUV32) was spin-coated on the coated wafer, baked on a hot plate at 90 ° C. for 60 seconds, and a film thickness of 0.7
The resist film was 2 μm. The resist film on this substrate is subjected to a Nikon KrF excimer laser reduction projection exposure apparatus (N
(A = 0.42), and baked on a hot plate at 110 ° C. for 60 seconds. After that, the resist film is coated with tetramethylammonium hydroxide 2.38.
Development was performed for 60 seconds with a weight% aqueous solution. By observing the resist pattern obtained after this development with a scanning electron microscope, the sensitivity, that is, the exposure amount (hereinafter referred to as E0) at which a 0.30 μm line and space is resolved 1: 1 and the resolution (hereinafter referred to as E0) The critical resolution at the exposure amount E0) and the pattern profile were evaluated. Table 2 shows the difference between the resist film thickness before exposure after baking and the film thickness of the unexposed portion after development together with the results of sensitivity and resolution. A small difference in film thickness indicates that thermal crosslinking proceeds and as a result, the dissolution contrast between the exposed and unexposed portions is large.

Example 2 The crosslinking agent was changed from 0.02 g of the crosslinking agent (a) to 0.1% of the crosslinking agent (b).
A liquid was prepared and evaluated in the same manner as in Example 1 except that the amount was changed to 02 g. Example 3 The crosslinking agent was changed from 0.02 g of the crosslinking agent (a) to 0.1 g of the crosslinking agent (c).
A liquid was prepared and evaluated in the same manner as in Example 1 except that the amount was changed to 02 g. Example 4 The crosslinking agent was changed from 0.02 g of the crosslinking agent (a) to 0.1% of the crosslinking agent (d).
A liquid was prepared and evaluated in the same manner as in Example 1 except that the amount was changed to 02 g.

Example 5 The crosslinking agent was changed from 0.02 g of the crosslinking agent (a) to 0.1% of the crosslinking agent (e).
A liquid was prepared and evaluated in the same manner as in Example 1 except that the amount was changed to 02 g. Example 6 The crosslinking agent was changed from 0.02 g of the crosslinking agent (a) to 0.1% of the crosslinking agent (f).
A liquid was prepared and evaluated in the same manner as in Example 1 except that the amount was changed to 02 g.

Comparative Example 1 A resist photosensitive solution was prepared and evaluated in the same manner as in Example 1 except that 0.02 g of the compound CL1 was used as a thermal crosslinking agent, and the evaluation results are shown in Table 2. When the photosensitive liquid of Comparative Example 1 was used, the 0.3 μ pattern resolved at the exposure amount E ₀ had a sharp corner and was inferior in shape. Comparative Example 2 A resist photosensitive solution was prepared in the same manner as in Example 1 except that 0.02 g of the compound CL2 was used as a thermal crosslinking agent, and the evaluation results are shown in Table 2. . When the photosensitive solution of Comparative Example 2 was used, the 0.3 μ pattern resolved at the exposure amount E ₀ had a sharp corner and was inferior in shape.

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[Table 2]

In the examples, the amount of film loss in the unexposed areas is smaller than in the comparative examples, and the thermal crosslinking is more advanced. In addition, the rectangularity was obviously improved, and the resolving power was also improved.

[0081]

According to the radiation-sensitive composition of the present invention, a specific cross-linking agent is used as a component thereof, thereby improving the resolving power as compared with the conventional one while maintaining sufficient storage stability in the form of a resist liquid. The properties are very good. In addition, the above-mentioned effect is achieved under a shorter temperature and a lower temperature and more advantageous process conditions in terms of throughput, so that it is extremely useful in practical use.

Claims (9)

[Claims] (1) an alkali-soluble resin or a resin having an acid-decomposable protecting group in at least a part of an alkali-solubility-imparting group of the resin; and (b) at least two resins per molecule.
A radiation-sensitive composition comprising a compound having two or more acyloxyalkoxy groups. 2. The radiation-sensitive composition according to claim 1, wherein the radiation-sensitive composition further comprises (c) an acid generator that generates an acid by the action of radiation. 3. The radiation-sensitive composition according to claim 1, wherein the acyloxyalkoxy group is a compound represented by the following general formula (1). Embedded image (Wherein, R ^{1 to} R ³ independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group,
Or an alkenyl group which may be substituted. ) 4. The heat-sensitive radiation composition according to claim 3, wherein R ² is a hydrogen atom or an optionally substituted alkyl group, and R ³ is an optionally substituted alkyl group. . 5. A compound having 1 to 1 carbon atoms, wherein R ¹ may be substituted.
20 alkyl groups or aryl groups, wherein R ² is a hydrogen atom or an unsubstituted alkyl group having 1 to 10 carbon atoms,
R ³ is 3. The radiation-sensitive composition, wherein the unsubstituted alkyl group having 1 to 10 carbon atoms. 6. R ² is a hydrogen atom or a methyl group,
Claim R ³ is characterized in that it is a group of the formula 3-5
The radiation-sensitive composition according to any one of the above. Embedded image (Wherein, R ³¹ and R ³² independently represent a hydrogen atom or a group having 1 to 1 carbon atoms)
And represents an alkyl group of 0. ) 7. An acid-decomposable protecting group represented by the following general formula (2):
The radiation-sensitive composition according to any one of claims 1 to 6, wherein the radiation-sensitive composition is at least one of the groups represented by (3) and (4). Embedded image (Wherein, R ^{4 to} R ⁸ are each independently a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ and R ⁶ may be bonded to form a ring. R ⁹ and R ¹⁰ are independently Represents an alkyl group.) 8. The radiation-sensitive resin according to claim 1, wherein the resin having an acid-decomposable protecting group as a part of the alkali-solubility-providing group is represented by the following general formula (5). Composition. Embedded image (Wherein T ¹ , T ² and T ³ are groups represented by the general formula (2), (3) or (4) according to claim 7)
T ¹ , T ² and T ³ are different groups. Z ^{1 to} Z
⁸ independently represents a hydrogen atom or a methyl group. w, x and y
Is 0 or a positive number, respectively, w, x, and y do not become 0 at the same time, and z is a positive number. W, x,
y and z are 0 ≦ w / (w + x + y + z) ≦ 0.5 and 0 ≦ x
/(W+x+y+z)≦0.5, 0 ≦ y / (w + x + y
+ Z) ≦ 0.5, 0.4 ≦ z / (w + x + y + z) ≦
Satisfies the relationship of 0.9. ) 9. With respect to 100 parts by weight of the resin of the component (a),
0.5 to 30 parts by weight of the compound of component (b), component (c)
The radiation-sensitive composition according to any one of claims 2 to 8, comprising 1 to 10 parts by weight of the acid generator.