JPH09218512A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the generation of scum and to ensure superior sensitivity and resolution as well as superior developability and a favorable pattern shape by incorporating an alkali-soluble resin and a specified 1,2-quinonediazido compd. SOLUTION: This compsn. contains an alkali-soluble resin and a 1,2- quinonediazido compd. represented by the formula, wherein R01 is H or alkyl, R02 is alkyl or aryl, each of X1 -X18 is H, halogen, alkyl,. cycloalkyl, alkoxyl, aryl or a group represented by -OD (D is H or an org. group having a 1,2- quinonediazo group), at least one of X1 -X5 , at least one of X6 -X9 , at least one of X10 -X13 , and at least one of X14 -X18 are groups represented by -OD, and one of D's of the groups represented by -OD is an org. group having a 1,2- quinonediazido group and A is a single bond.

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to a radiation-sensitive resin composition containing an alkali-soluble resin. More specifically, various radiations such as ultraviolet rays such as g-rays and i-rays, far ultraviolet rays such as a KrF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams, in particular, high sensitivity to ultraviolet rays and far ultraviolet rays. The present invention relates to a radiation-sensitive resin composition suitable as a resist for producing an integrated circuit.

[0002]

2. Description of the Related Art Positive resists are often used in the manufacture of integrated circuits. With the recent trend toward higher integration of integrated circuits, positive resists capable of forming resist patterns with higher resolution are desired. ing. In order to improve the resolution of the positive resist, there is a method of improving the resist material, for example, a method of reducing the molecular weight of the alkali-soluble resin used in the resist, but in this case, there is a problem that the heat resistance of the resist decreases. Occurs. Further, as a method of improving the resolution by the process improvement, there is a method of increasing the aperture coefficient (NA) of the stepper, but in this case, there is a problem that the depth of focus (focus tolerance) becomes narrow, and at the same time, the resist material Improvement is needed. For example, increasing the addition amount of the quinonediazide compound in order to improve the focus tolerance is one of the countermeasures, but increasing the addition amount of the quinonediazide compound deteriorates the developability. in this way,
Since positive performance of one resist decreases when another performance is improved, it is desired to develop a positive resist having high resolution, good focus tolerance and good developability for fine patterns at the same time. There is.

Japanese Unexamined Patent Publication No. 6-167805 discloses an alkali-soluble resin and the following formula (2)

[0004]

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[In the formula (2), R ₁ represents a hydrogen atom or a halogen atom, R ₃ represents an alkyl group or a phenyl group, x is 1 to 3, Q _{1 to} Q ₁₂ are hydrogen atoms, Is an alkyl group or a phenyl group, and Z _{1 to} Z ₅ are

[0006]

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(In the formula, R ₂ represents a hydrogen atom or a halogen atom, R ₃ has the same meaning as described above, and y is 1
To 3 and p is 0 to 1)], and a positive resist composition containing a quinonediazide sulfonic acid ester of a compound represented by the formula as a photosensitizer.
JP-A-7-104465 discloses an alkali-soluble resin and the following formula (3)

[0008]

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[In the formula (3), R ^{1 to} R ¹⁰ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group,
An aryl group, an alkoxyl group, an acyl group, an alkenyl group, a nitro group or a cyano group, and a, b, c and d are 1 or 2 (provided that a + c = b + d =
4) and n represents 4 or 5], and a positive resist composition containing a quinonediazide sulfonic acid ester of a compound represented by the formula as a photosensitizer is disclosed.

Further, JP-A-7-159990 discloses that an alkali-soluble phenol resin and the following formula (4)

[0011]

[Chemical 6]

[In the formula (4), k is 1 or 2, and m is
Is 1 or 2, and R ^{11 to} R ¹⁴ are the same or different and each is a halogen atom, an alkyl group, an alkenyl group,
An alkoxy group, an aryl group or an acyl group, R
^{15 to} R ²⁰ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an aryl group or an acyl group, X is a single bond,
O -, - S -, - SO -, - SO 2 -, - CO -, - C
O ₂ -, cyclopentylidene, cyclohexylidene, phenylene,

[0013]

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(In the formula, R ²¹ and R ²² are the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group,
An aryl group or a substituted aryl group),

[0015]

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(Wherein R ^{23 to} R ²⁶ are the same or different and each is a hydrogen atom or an alkyl group, and n is 1 to 1).
An integer of 5), or

[0017]

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(Wherein R ^{27 to} R ³⁰ are the same or different and each is a hydrogen atom or an alkyl group) and a quinonediazide sulfonic acid ester of the compound represented by Type resist compositions are disclosed.

However, the positive resist compositions disclosed in these publications are well balanced in sensitivity, resolution, developability, heat resistance, pattern shape, exposure margin, and focus allowance, and each characteristic is further improved by one step. It was not obtained as a composition.

[0020]

An object of the present invention is to provide a novel radiation-sensitive resin composition. Another object of the present invention is to positively resist the generation of scum effectively, obtain an excellent developability, obtain a good pattern shape, and also an excellent sensitivity and resolution, and a particularly good exposure margin. It is to provide a suitable radiation-sensitive resin composition. Further objects and advantages of the present invention will be apparent from the following description.

[0021]

According to the present invention, the above objects and advantages of the present invention are achieved by using an alkali-soluble resin and the following formula (1).

[0022]

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[In the formula (1), R ₀₁ is a hydrogen atom or an alkyl group, R ₀₂ is an alkyl group or an aryl group, X _{1 to} X ₁₈ are the same or different from each other, and are hydrogen atoms. , A halogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an aryl group or a group represented by -OD (wherein D is a hydrogen atom or an organic group containing a 1,2-quinonediazide group). Where X
_At least one of _{1 to} X ₅ , at least one of X _{6 to} X ₉ ,
At least one of X _{10 to} X ₁₃ and at least one of X _{14 to} X ₁₈ is a group represented by —OD, and at least one of a plurality of D of these groups represented by —OD is 1,2- It is an organic group containing a quinonediazide group. A is
Single bond, -O-, -S-, -C (= O)-, -S (=
O) -or

[0024]

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[Wherein, Y ₁ and Y ₂ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group]]
This is achieved by a radiation-sensitive resin composition containing a quinonediazide compound.

The present invention will be specifically described below, but the purpose, constitution and effect of the present invention will be clarified by this.

Alkali-Soluble Resin The alkali-soluble resin used in the present invention (hereinafter,
It is called “resin (A)”. Examples of the) include novolac resin, polyvinylphenol or its derivative, styrene-maleic anhydride copolymer or its derivative, polyvinylhydroxybenzoate, and carboxyl group-containing (meth) acrylic acid-based resin. The resin (A) may be the resin represented by the above-mentioned examples alone or 2
It can be used in combination of more than one kind. Preferred resins (A) include novolak resins. Such novolac resin has the following formula (5)

[0028]

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[In the formula (5), n is an integer of 1 to 3]
It is obtained by polycondensing the phenols represented by and the aldehydes represented by a monoaldehyde compound or a bisaldehyde compound.

Examples of the above-mentioned phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3, and
4-xylenol 3,5-xylenol, 2,3,5-
Examples include trimethylphenol, 3,4,5-trimethylphenol and the like. In particular, m-cresol, p
-Cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol are preferred. These phenols are used alone or in combination of two or more. When two or more phenols are used in combination, for example, m-cresol / p-cresol = 3
0-95 / 5-70 (weight ratio), m-cresol / 2,
3-xylenol / 3,4-xylenol = 20 to 95
/ 5-80 / 0-75 (weight ratio), or m-cresol / 2,3,5-trimethylphenol / 2,3-xylenol = 20-95 / 5-80 / 0-75 (weight ratio) combination Is particularly preferable.

Examples of monoaldehydes to be polycondensed with the phenols include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde,
β-phenylpropyl aldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-
Hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-
Examples include methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural and the like. Examples of bisaldehydes include glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde and the like. Of these, formaldehyde can be particularly preferably used.

Examples of the formaldehyde include formaldehydes such as formalin, trioxane, and paraformaldehyde, hemiformals such as methyl hemiformal, ethyl hemiformal, propyl hemiformal, butyl hemiformal, and phenyl hemiformal, or o-hydroxybenzaldehyde. , Benzaldehydes such as m-hydroxybenzaldehyde and p-hydroxybenzaldehyde can be used as the raw material. Of these, formalin, butyl hemiformal and o-hydroxybenzaldehyde are particularly preferably used. These aldehydes can be used alone or in combination of two or more.
The amount of the aldehyde used is preferably 0.7 to 3 mol, more preferably 0.6 to 3 mol per mol of the phenol.
1.5 moles.

An acidic catalyst is usually used in the polycondensation reaction of phenols and aldehydes. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid,
Acetic acid, p-toluenesulfonic acid and the like can be mentioned. The amount of these acidic catalysts used is usually 1 × 10 ^{−5 to} 5 × 10 ⁻¹ mol per mol of phenols.

In the polycondensation reaction, water is usually used as the reaction medium, but when the phenols used in the reaction do not dissolve in the aqueous solution of aldehydes and become a heterogeneous system from the initial stage of the reaction, the reaction A hydrophilic solvent can also be used as the medium. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is
Usually, it is 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material. The reaction temperature of the polycondensation can be appropriately adjusted according to the reactivity of the raw materials, but is usually from 10 to 200 ° C.

As the polycondensation reaction method, a method in which phenols, aldehydes, an acidic catalyst and the like are charged all at once, and a method in which phenols, aldehydes and the like are added in the presence of an acidic catalyst as the reaction progresses, etc. It can be appropriately adopted. After completion of the polycondensation reaction, in order to remove unreacted raw materials, acidic catalyst, reaction medium, etc. present in the system, generally, the reaction temperature is raised to 130 ° C to 230 ° C,
Volatiles are removed under reduced pressure and the novolak resin is recovered.

The polystyrene-equivalent weight average molecular weight of the novolak resin used in the present invention (hereinafter referred to as "Mw")
That. ) Is preferably 2,000 to 20,000, from the viewpoints of workability when applying the composition of the present invention to a substrate, developability when used as a resist, sensitivity and heat resistance, and preferably 3). It is particularly preferable that it is 1,000 to 15,000. In order to obtain a novolak resin having a particularly high Mw, the novolak resin obtained by the above method is used, for example, ethylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, methyl isobutyl ketone, dioxane, methanol, ethyl acetate. After dissolving in a good solvent such as, for example, water, a poor solvent such as n-hexane, n-heptane, or the like is mixed, and then the precipitated resin solution layer is separated to recover a high molecular weight novolak resin.

Dissolution accelerator In the present invention, a low molecular weight phenol compound (hereinafter,
It is referred to as "dissolution promoter." ) Can be added. As the dissolution promoter, the number of benzene rings in the molecule is 2 to 5
Phenolic compounds are suitable, for example, the following formula (6
The compounds represented by -1) to (6-9) can be exemplified.

[0038]

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[0039]

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[In the formulas (6-1) to (6-9), a, b
And c are each a number from 0 to 3 (except when both are 0), and x, y and z are 0 to 0, respectively.
A number of 3 and a + x ≦ 5, b + y ≦ 5 and c
+ Z ≦ 5 (however, b + y ≦ 4 for (6-3) and (6-4)). ] The content of such a dissolution accelerator is usually 100% of resin (A).
It is 50 parts by weight or less per part by weight.

Other Alkali-Soluble Resin In the present invention, a part of the resin (A) is referred to as a low-molecular weight alkali-soluble resin (hereinafter referred to as “resin (B)”) for the purpose of promoting the alkali-solubility of the resin (A). ) Can be changed. Examples of the resin (B) include an alkali-soluble novolac resin. These are obtained by the reaction of polycondensation of the above-mentioned phenols and aldehydes. As the phenols, 1-naphthol, 2-naphthol and the like can be used in addition to those exemplified as the phenols used in the synthesis of the novolak resin. Further, as the aldehydes, those used in the synthesis of the novolak resin can be used. In this case, the amount of aldehydes used is usually 0.2 to 0.8 with respect to 1 mol of phenols.
Is a mole. In this polycondensation reaction, an acidic catalyst used for producing a novolac resin can be used.

The Mw of the resin (B) is 300 to 2,000.
It is preferably less than 500, and more preferably 500 to 1,000. As such a resin (B),
Examples thereof include phenol / formaldehyde condensation resin, o-cresol / formaldehyde condensation resin, m-cresol / formaldehyde condensation resin, p-cresol / formaldehyde condensation resin, m-cresol / p-cresol / formaldehyde condensation resin. The amount of the resin (B) compounded is generally such that the resin (A) and the resin (B) are mixed.
Of 50 parts by weight or less in 100 parts by weight in total.

1,2-quinonediazide compound The composition of the present invention contains a compound represented by the above formula (1) as a 1,2-quinonediazide compound. In formula (1), R ₀₁ is a hydrogen atom or an alkyl group.
Here, the alkyl group is preferably an alkyl group having 1 to 2 carbon atoms, and specific examples thereof include a methyl group and an ethyl group. In formula (1), R ₀₂ is an alkyl group or an aryl group. Here, as the alkyl group,
An alkyl group having 1 to 4 carbon atoms is preferable, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. The aryl group has 6 to 6 carbon atoms.
The aryl group of 10 is preferable, and specific examples thereof include a phenyl group, a toluyl group and a naphthyl group.

In the formula (1), X _{1 to} X ₁₈ are the same or different from each other and are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an aryl group or a group represented by --OD (here And D is a hydrogen atom or an organic group containing a 1,2-quinonediazide group)
It is. However, at least one of X _{1 to} X ₅ , at least one of X _{6 to} X ₉ , at least one of X _{10 to} X ₁₃ , and at least one of X _{14 to} X ₁₈ are a group represented by —OD. is there.

Here, as the halogen atom, specifically, a chloro atom, a bromine atom and the like can be exemplified.
As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and the like. You can Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. As the alkoxyl group, an alkoxyl group having 1 to 4 carbon atoms is preferable, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Further, as the aryl group, an aryl group having 6 to 10 carbon atoms is preferable, and specific examples thereof include a phenyl group, a toluyl group and a naphthyl group.

In the formula (1), A is a single bond, -O-, -S.
-, -C (= O)-, -S (= O)-or

[0047]

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(In the formula, Y ₁ and Y ₂ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group). Where the carbon number is 1 to 4
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and the like.

Examples of the organic group containing a 1,2-quinonediazide group in the above D include, for example, 1,2-benzoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-4-sulfonyl group and 1,2-naphthogroup. A preferable example is a 1,2-quinonediazidesulfonyl group such as a quinonediazide-5-sulfonyl group and a 1,2-naphthoquinonediazide-6-sulfonyl group.
The 1,2-naphthoquinonediazide-4-sulfonyl group and the 1,2-naphthoquinonediazide-5-sulfonyl group are particularly preferred. In the formula (1), the compound corresponding to the case where all D are hydrogen atoms, that is, the compound corresponding to the case where the group represented by -OD is a hydroxyl group is a precursor of the compound represented by the formula (1). Yes (hereinafter, referred to as “compound (a)”). Specific examples of the compound (a) include compounds represented by the following formulas (7-1) to (7-23).

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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The compound (a) which is the precursor is represented by the following formula (8).

[0056]

[Chemical 21]

Here, X _{1 to} X ₉ are the same or different from each other and are a hydrogen atom, a halogen atom, an alkyl group,
It is a cycloalkyl group, an alkoxyl group, an aryl group or a hydroxyl group. However, at least one of X _{1 to} X ₅ and X
_At least one of _{6 to} X ₉ is a hydroxyl group. The definition of A is the same as in formula (1), and a phenol compound represented by the following formula (9)

[0058]

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Here, the definitions of R ₀₁ and R ₀₂ are the same as in formula (1). R ₀₁ is preferably a hydrogen atom, and an α, β-diketone compound represented by
It can be produced by reacting in the presence of sulfuric acid, p-toluenesulfonic acid or the like.

The phenol compound of formula (8) may be used alone or in combination of two or more. The reaction is usually of the formula (8)
The diketone of the formula (9) is used in a ratio of about 1 mol per 2 mol of the compound.

Specific examples of the compound represented by the formula (1) (hereinafter referred to as "compound (b)") include:
1,2-benzoquinonediazide-4-sulfonic acid ester of compound (a) represented by (7-1) to (7-23), 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphtho Examples thereof include quinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazide-6-sulfonic acid ester. Especially 1,2-
Naphthoquinonediazide-4-sulfonate and 1,2-naphthoquinonediazide-5-sulfonate are preferred.

The compound (b) can be obtained, for example, by reacting the compound (a) with 1,2-naphthoquinonediazide-4-sulfonyl chloride in the presence of a basic catalyst.

In the composition of the present invention, the compound (b)
Is preferably used in an amount of 5 to 50 parts by weight, particularly 10 to 40 parts by weight, per 100 parts by weight of the resin (A). The compound (b) can be used alone or in combination of two or more kinds.

In the present invention, 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester other than compound (b) is used in combination with compound (b). A 1,2-quinonediazide compound such as 2,2-naphthoquinonediazide-5-sulfonic acid ester can be added. Examples of such 1,2-quinonediazide compounds include 2,3,
4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2 ', 4'-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, 1,3,5- Tris (4-hydroxy-α, α-dimethylbenzyl) benzene, 1,1-bis- (4-hydroxyphenyl) -1- [4- {1- (4
-Hydroxyphenyl) -1-methylethyl} phenyl] ethane, 2- (3,4-dihydroxyphenyl)-
2- (4-hydroxyphenyl) propane, 2,4,4-
Trimethyl-2- (2,4-dihydroxyphenyl)-
Examples thereof include 1,2-quinonediazide sulfonic acid ester such as 7-hydroxychroman.

In the composition of the present invention, the compounding amount of the 1,2-quinonediazide compound other than the compound (b) is preferably 100 parts by weight or less with respect to 100 parts by weight of the resin (A). Further, 1,2-occupying in the composition of the present invention
The total weight of the quinonediazide sulfonyl residue is adjusted to be 5 to 50% by weight, and more preferably 10 to 30% by weight, as a ratio to the total solid content of the composition.

Various Compounding Agents Various additives such as a sensitizer and a surfactant can be compounded in the composition of the present invention, if necessary. The sensitizer is added to improve the sensitivity of the resist. Examples of such a sensitizer include 2H-pyrido- [3,2-b] -1,4-oxazine-3 (4H)-.
Ons, 10H-pyrido- [3,2-b]-(1,4 ')
-Benzothiazines, urazoles, hydantoins,
Examples include parbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, and maleimides. The compounding amount of these sensitizers depends on the resin (A)
It is preferably 50 parts by weight or less with respect to 100 parts by weight.

The surface active agent is added to improve the coatability and developability of the composition. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, Megafax F17.
1, F172, F173 (trade name, manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (trade name, manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-.
103, SC-104, SC-105, SC-106
(Brand name, manufactured by Asahi Glass Co., Ltd.), KP341 (Brand name, manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, No. 95 (Brand name, manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.), NBX-15 (Brand name, Neos Co., Ltd.) Manufactured) and the like. The blending amount of these surfactants is 100% of solid content of the composition excluding various blending agents.
The amount of the active ingredient of the surfactant is preferably 2 parts by weight or less per part by weight.

Further, in the composition of the present invention, a dye or a pigment can be blended in order to visualize the latent image in the radiation-irradiated portion of the resist and reduce the effect of halation at the time of radiation irradiation. It is also possible to add an adhesion aid to improve the above. Further, if necessary, a storage stabilizer, a defoaming agent, etc. may be added.

Solvent The composition of the present invention contains the above solid content of the resin (A),
For example, it is prepared by dissolving it in a solvent so that the solid content concentration becomes 20 to 40% by weight, and filtering with a filter having a pore size of about 0.2 μm.

Examples of the solvent used in this case include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether. Acetate, propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, 2-
Heptanone, 3-heptanone, 4-heptanone, cyclohexanone, ethyl 2-hydroxypropionate, 2-
Ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-
Examples thereof include methyl 3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate and the like. Furthermore, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-
Methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate. It is also possible to add a high boiling point solvent such as γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate. These solvents are used alone or in combination of two or more.

The composition of the present invention prepared as a solution for forming a resist film is applied to a silicon wafer or a wafer coated with aluminum by spin coating, cast coating, roll coating or the like. Next, a resist film is formed by pre-baking the resist film, and the resist film is irradiated with radiation so as to form a desired resist pattern, and is developed with a developer to form a pattern. As the radiation used at this time, ultraviolet rays such as g-rays and i-rays are preferably used, but far-ultraviolet rays such as excimer lasers, X-rays such as synchrotron radiation, and various radiations such as charged particle beams such as electron beams are used. You can also

Further, the composition of the present invention, after forming a resist film, prebaking and irradiation with radiation,
The effect of the present invention can be further improved by performing an operation of heating at 140 ° C. (hereinafter, referred to as “post-baking”) and then performing development. Examples of the developer used for the resist film include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propyl. Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- (5.4.0) -7
-Undecene, 1,5-diazabicyclo- (4.3.0)
An alkaline aqueous solution obtained by dissolving an alkaline compound such as -5-nonane in water to a concentration of, for example, 1 to 10% by weight is used.

The developer contains a water-soluble organic solvent,
For example, an appropriate amount of an alcohol such as methanol or ethanol or a surfactant may be used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

[0074]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The measurement of Mw and the evaluation of the resist in the examples were performed by the following methods.

Mw: Tosoh GPC column (G200
0H _XL : 2 pieces, G3000H _XL : 1 piece, G4000
H _XL (1 bottle), flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C., analysis conditions were determined by gel permeation chromatography using monodisperse polystyrene as a standard.

Resolution: The minimum size of a line-and-space pattern that is separated without reducing the film thickness by the exposure amount when resolving a 0.4-μm line-and-space pattern one-to-one. It was measured at.

Developability: forming a resist film of the composition,
The scum after pattern formation and the degree of residual development were examined using a scanning electron microscope.

Focus Tolerance: A swing width of focus when a pattern dimension resolved in a 0.4 μm line-and-space pattern is within ± 10% of a mask design dimension using a scanning electron microscope. Was used as the focus range and was used as the evaluation index. A large focus range means that it has good focus tolerance.

Exposure margin: When the line and space pattern of 0.4 μm begins to be resolved when the exposure amount (E _OP ) when the line and space pattern of 0.4 μm is resolved one to one A value obtained by dividing the exposure amount (E _c ) is used as an exposure margin, and a large value means that the exposure margin is good.

Pattern shape: The exposure amount for resolving a 0.4 μm line-and-space pattern in a one-to-one manner, and a cross section of the 0.4 μm pattern was observed with a scanning electron microscope. The shapes are represented as (G) and (A).

<Synthesis of Resin (A)> Synthesis Example 1 In an autoclave, m-cresol 64.9 g (0.6 mol) 2,3-xylenol 36.7 g (0.3 mol) 3,4-xylenol 12. 2 g (0.1 mol) 37% by weight aqueous formaldehyde solution 77.1 g (formaldehyde: 0.9 mol) oxalic acid dihydrate 6.3 g (0.05 mol) Water 79.4 g and dioxane 383.9 g were charged, Immerse the autoclave in an oil bath and adjust the internal temperature to 130
After carrying out condensation for 8 hours while maintaining the temperature at ℃ and stirring,
After cooling to room temperature, the contents were taken out into a beaker. After separating into two layers in this beaker, the lower layer was taken out, concentrated, dehydrated, and dried to recover the novolak resin. This resin is referred to as resin (A1). The Mw of the resin (A1) is
It was 8,600.

Synthesis Example 2 In an autoclave, m-cresol 64.9 g (0.6 mol) 2,3-xylenol 36.7 g (0.3 mol) 2,3,5-trimethylphenol 13.6 g (0.1 mol) 37% by weight formaldehyde aqueous solution 77.1 g (formaldehyde: 0.9 mol) Oxalic acid dihydrate 6.3 g (0.05 mol) Water 79.4 g and dioxane 383.9 g were charged, and the same as in Synthesis Example 1. Was performed to synthesize a novolak resin. This resin is referred to as resin (A2). The Mw of the resin (A2) was 8,800.

<Synthesis of Compound (b)> In the following, the compound represented by the formula (6-6) is (a-1) and the compound represented by the formula (7-7) is (a-2). The compound represented by the formula (7-18) is abbreviated as (a-3).

Synthesis Example 3 In a flask equipped with a stirrer, a dropping funnel and a thermometer, protected from light, 24.3 g (0.05 mol) of the compound of (a-1) 1,2-naphthoquinonediazide-5-sulfone was added. 53.7 g (0.20 mol) of acid chloride and 468 g of dioxane were charged and dissolved with stirring. Then, the flask was immersed in a water bath controlled at 30 ° C., and the internal temperature was adjusted to 3
When the temperature became constant at 0 ° C., 22.2 g (0.22 mol) of triethylamine was added to this solution using a dropping funnel so that the internal temperature did not exceed 35 ° C., and the reaction was carried out at the same temperature for 2 hours. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of a dilute hydrochloric acid aqueous solution to precipitate a reaction product.
The precipitate is then filtered, collected and placed in a vacuum oven at 40 ° C.
After that, it was dried overnight to obtain a quinonediazide compound (b-1).

Synthesis Example 4 27.1 g (0.05 mol) of the compound of (a-2) 1,2-naphthoquinonediazide-5-sulfonyl chloride 53.7 g (0.20 mol) dioxane 485 g and triethylamine 22.2 g ( A quinonediazide compound (b-2) was obtained in the same manner as in Synthesis Example 3 except that 0.22 mol) was used.

Synthesis Example 5 Compound of (a-3) 27.4 g (0.05 mol) 1,2-naphthoquinonediazide-5-sulfonyl chloride 53.7 g (0.2 mol) dioxane 487 g and triethylamine 22.2 g ( A quinonediazide compound (b-3) was obtained in the same manner as in Synthesis Example 3 except that 0.22 mol) was used.

<Synthesis of Other Quinonediazide Compounds> Synthesis Example 6 Tris (4-hydroxyphenyl) methane 14.6 g (0.05 mol) 1,2-naphthoquinonediazide-5-sulfonyl chloride 33.5 g (0.125 mol) ) A quinonediazide compound (a) was obtained in the same manner as in Synthesis Example 3 except that 288 g of dioxane and 13.9 g (0.138 mol) of triethylamine were used.

Synthesis Example 7 1,1-bis (4-hydroxy-2,5-dimethylphenyl) acetone 14.9 g (0.05 mol) 1,2-naphthoquinonediazide-5-sulfonyl chloride 20.1 g (0.1 mol) A quinonediazide compound (II) was obtained in the same manner as in Synthesis Example 3 except that 210 g of dioxane and 8.4 g (0.083 mol) of triethylamine were used.

Examples 1 to 6 Resin (A), a dissolution accelerator, a quinonediazide compound and a solvent were mixed at the composition ratios shown in Table 1 (however, parts are parts by weight) to prepare a uniform solution. A solution of the composition was prepared by filtering with a membrane filter having a pore size of 0.2 μm. The obtained solution was applied onto a silicon wafer having a silicon oxide film by using a spinner, and then prebaked at 90 ° C. for 2 minutes on a hot plate to have a thickness of 1.
A 1 μm resist film was formed. Then, through a reticle, a NSR-2005i9C reduction projection exposure machine (lens numerical aperture = 0.57) manufactured by Nikon Corporation was used to obtain a wavelength of 365n.
Exposure was performed using m (i-line), development was performed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution, rinsed with ultrapure water, and drying was performed to form a resist pattern. The obtained resist pattern was examined and the characteristics of the composition of each example as a resist pattern were evaluated. The results are shown in Table 1.

[0090]

[Table 1]

In Table 1, the types of the dissolution accelerator and the solvent are as follows. Dissolution accelerator α: 1,1,1-tris (4-hydroxyphenyl) ethane, β: 1,1-bis (4-hydroxyphenyl) -1-phenylethane, γ: 1,1-bis (4-hydroxy) -2,5-Dimethylphenyl) acetone Solvent S1: Ethyl 2-hydroxypropionate, S2: Methyl 3-methoxypropionate, S3: Methyl-n-amyl ketone

[0092]

EFFECTS OF THE INVENTION The radiation-sensitive resin composition of the present invention effectively suppresses the generation of scum, excels in developability, obtains a good pattern shape, and has a high resolution, in particular, focus tolerance and exposure. The margin is improved. for that reason,
The radiation-sensitive resin composition can be suitably used as a resist for producing an integrated circuit having a high degree of integration.

The preferred embodiments of the present invention will be described below. 1. A radiation-sensitive resin composition containing an alkali-soluble resin and a 1,2-quinonediazide compound represented by the above formula (1). 2. The alkali-soluble resin is selected from the group consisting of novolac resin, polyvinylphenol or its derivative, styrene-maleic anhydride copolymer or its derivative, polyvinylhydroxybenzoate and carboxyl group-containing (meth) acrylic acid-based resin. The composition as described. 3. The above 1,2-quinonediazide compound is represented by the above formula (6-
1,2-benzoquinonediazide-4-sulfonic acid ester of the compound represented by 1) to (6-23), 1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 1,
The composition according to 1 above, which is selected from the group consisting of 2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazide-6-sulfonic acid ester. 4. The composition according to 1 above, wherein 5 to 50 parts by weight of the 1,2-quinonediazide compound is used per 100 parts by weight of the alkali-soluble resin. 5. The composition according to 1 above, which further contains a dissolution accelerator selected from the group consisting of phenol compounds represented by the formulas (6-1) to (6-9).

[Brief description of drawings]

FIG. 1 is a diagram showing a cross-sectional shape of a resist pattern.

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Akira Tsuji 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd.

Claims (1)

[Claims] 1. An alkali-soluble resin and the following formula (1): [In the formula (1), R ₀₁ represents a hydrogen atom or an alkyl group, R ₀₂ represents an alkyl group or an aryl group, and X ₁
To X ₁₈ are the same or different from each other, and each is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an aryl group or a group represented by -OD (wherein D is a hydrogen atom or 1,2- It is an organic group containing a quinonediazide group). However, at least one of X _{1 to} X ₅ , at least one of X _{6 to} X ₉ , and X _{10 to} X.
_At least one of ₁₃ and at least one of X _{14 to} X ₁₈ is a group represented by -OD, and at least one of a plurality of D of the groups represented by -OD contains a 1,2-quinonediazide group. Is an organic group. A is a single bond,
-O-, -S-, -C (= O)-, -S (= O)-or (Wherein Y ₁ and Y ₂ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group)], and a 1,2-quinonediazide compound is contained. A radiation-sensitive resin composition comprising: