JP3064286B2 - Negative radiation-sensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a negative-working radiation-sensitive resin composition. More specifically, UV, far UV, X
The present invention relates to a negative-type radiation-sensitive resin composition suitable as a negative-type resist for producing an integrated circuit, which is sensitive to radiations such as rays, electron beams, molecular beams, γ rays, synchrotron radiation, and proton beams.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, development of a lithography process capable of microfabrication of 0.5 μm or less has recently been advanced. I have.

As one of means for improving resolution in a lithography process, a method of shortening the wavelength of radiation to be irradiated, for example, a KrF excimer laser (248n
m) and the like. As a resist suitable for this deep ultraviolet ray, a chemically amplified resist has been proposed. The resist generates an acid in the resist film by irradiation with radiation, causes a chemical reaction by the acid, changes the solubility in a developing solution, and forms a pattern during development. However, the conventional chemically amplified negative resist has a drawback that the resist pattern absorbs a developing solution and swells. Such a swelling phenomenon undesirably causes a reduction in resolution and causes a pattern to meander.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a negative-type radiation-sensitive resin composition. Another object of the present invention is to provide a negative-type radiation-sensitive resin composition which can be suitably used for irradiation with a radiation having a wavelength equal to or less than far ultraviolet rays, and which is excellent in sensitivity, developability, resolution and the like. Still another object and advantage of the present invention is to provide a negative-type radiation-sensitive resin composition capable of effectively suppressing swelling and meandering of a resist pattern during development.

[0005]

According to the present invention, the above objects and advantages of the present invention are as follows: (1) a compound capable of generating an acid upon irradiation with radiation (hereinafter referred to as "acid generator");
(2) a crosslinking agent that undergoes a crosslinking reaction in the presence of an acid (hereinafter referred to as “crosslinking agent”), (3) an alkali-soluble resin, and (4) a structural formula (1) shown below

[0006]

Embedded image

This is achieved by a negative radiation-sensitive resin composition comprising a phenolic compound represented by the formula (hereinafter referred to as "compound (a)").

Hereinafter, the negative radiation-sensitive resin composition of the present invention will be described. Acid generator Examples of the acid generator used in the present invention include an onium salt, a haloalkyl group-containing compound, a quinonediazide compound, a β-ketosulfone compound, a β-sulfonylsulfone compound, a nitrobenzylsulfonate compound, and a sulfonic acid ester compound. Specifically, the following compounds can be exemplified.

Examples of the onium salts include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts and the like. Preferably, the following structural formula (2)

[0010]

Embedded image

A compound represented by the following structural formula (3)

[0012]

Embedded image

Here, the definitions of R ^11, R ¹² and X are the same as in the above structural formula (2).

And a compound represented by the following structural formula (4)

[0015]

Embedded image

Here, the definitions of R ¹¹ , R ¹² , R ¹³ and X are the same as in the above structural formula (2).

Compounds represented by the following formulas can be mentioned.

Examples of the haloalkyl group-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Preferably, the following structural formula (5)

[0019]

Embedded image

Here, R ¹⁸ is a trichloromethyl group, a phenyl group, a methoxyphenyl group, a naphthyl group or a methoxynaphthyl group.

A compound represented by the following formula (6):

[0022]

Embedded image

Here, R ¹⁹ , R ²⁰ and R ²¹ are the same or different and are a hydrogen atom, a halogen atom, a methyl group, a methoxy group or a hydroxyl group.

Compounds represented by the following formulas can be mentioned.

Examples of the quinonediazide compound include a diazobenzoquinone compound and a diazonaphthoquinone compound. Preferably, the following structural formula (7)

[0026]

Embedded image

A compound represented by the following structural formula (8)

[0028]

Embedded image

A compound represented by the following structural formula (9)

[0030]

Embedded image

A compound represented by the following structural formula (10):

[0032]

Embedded image

Compounds represented by the following formulas can be mentioned.

The β-ketosulfone compound and β-sulfonylsulfone compound are preferably represented by the following structural formula (11)

[0035]

Embedded image

Compounds represented by the following formulas can be mentioned.

The nitrobenzyl sulfonate compound is preferably a compound represented by the following structural formula (12)

[0038]

Embedded image

Compounds represented by the following formulas can be mentioned.

Examples of the sulfonic acid ester compound include an alkyl sulfonic acid ester, a haloalkyl sulfonic acid ester, an aryl sulfonic acid ester, and an imino sulfonic acid ester. Preferably, the following formula (13)

[0041]

Embedded image

Here, R ³⁵ and R ³⁶ are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³⁷ and R ³⁸ are the same or different and have a hydrogen atom and 1 to 4 carbon atoms. 4 alkyl groups or 6-20 carbon atoms
Is an aryl group of

A compound represented by the following formula (14)

[0044]

Embedded image

Here, R ³⁹ is a hydrogen atom or a compound having 1 to 1 carbon atoms.
And R ⁴⁰ and R ⁴¹ are the same or different and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 20 carbon atoms, or R ⁴⁰ and R ⁴¹ are bonded to each other. May form a ring together with the nitrogen atom to which they are attached,

And a compound represented by the following formula (1)
5)

[0047]

Embedded image

Here, Z is a fluorine atom, a chlorine atom, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a carbon atom having 6 to 14 carbon atoms.
Is an aryl group of

Compounds represented by the following formulas can be mentioned.

Of these, onium salts, quinonediazide compounds and haloalkyl group-containing compounds are preferred.
The mixing amount of these acid generators is 100
The amount is preferably 1 to 70 parts by weight, more preferably 3 to 50 parts by weight, and still more preferably 3 to 2 parts by weight with respect to parts by weight.
0 parts by weight. If the amount is less than 1 part by weight, it is difficult to obtain a sufficient pattern forming ability, and if it exceeds 70 parts by weight, scum tends to occur. The acid generators are used alone or in combination of two or more.

Crosslinking agent The crosslinking agent used in the present invention has a property of undergoing a crosslinking reaction with an alkali-soluble resin or the like in the presence of an acid. For example, the following structural formula (16)

[0052]

Embedded image

[0053] wherein R ⁴² is 1 to hydrogen atoms or carbon atoms
An alkyl group of 4,

A compound represented by the following formula (17)

[0055]

Embedded image

Here, R ⁴² is the same as defined in the above structural formula (16).

A compound represented by the following formula (18)

[0058]

Embedded image

Here, R⁴³Is an alkyl group having 1 to 4 carbon atoms
And R⁴⁴And R⁴⁵Are the same or different,
, An alkyl group having 1 to 4 carbon atoms or a phenyl group.
R ⁴⁶Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
A is a tyl group or a tetrahydropyranyl group;
B is an integer from 0 to 5, and b is an integer from 0 to 5,

A compound represented by the following formula (19)

[0061]

Embedded image

Here, the definitions of R ^{43 to} R ⁴⁶ are the same as those of the above structural formula (18), and R ⁴⁷ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acetyl group, a benzoyl group, a tetrahydropyrani A benzyl group, a nitrobenzyl group or a tosyl group, c is an integer of 1-5, and d is an integer of 0-4,

A compound represented by the following formula (20)

[0064]

Embedded image

A compound represented by the following formula (21)

[0066]

Embedded image

Here, R ⁴² is the same as defined in the structural formula (16).

A compound represented by the following formula (22)

[0069]

Embedded image

Here, R ⁴² is the same as defined in the above structural formula (16).

A compound represented by the following formula (23)

[0072]

Embedded image

And a compound represented by the following formula (2)
4)

[0074]

Embedded image

Here, R ⁵⁰ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen-substituted alkyl group having 1 to 4 carbon atoms.

Compounds represented by the following formulas can be mentioned. Among these, the compounds represented by the formulas (19), (20) and (23) are preferable.

The compounding amount of the crosslinking agent is as follows.
5 to 100 parts by weight, preferably 10 to 100 parts by weight
The amount is from 70 to 70 parts by weight, more preferably from 10 to 50 parts by weight. When the amount is less than 5 parts by weight, the swelling of the radiation-irradiated portion becomes large. On the other hand, if it exceeds 100 parts by weight, it becomes difficult to form a good pattern. The crosslinking agents may be used alone or as a mixture of two or more.

Alkali-Soluble Resin The alkali-soluble resin is not particularly limited as long as it has a property of being soluble in a developing solution composed of an alkaline aqueous solution. Examples of suitable alkali-soluble resins include novolak resins and polyhydroxystyrene resins. Is mentioned.

The novolak resin is obtained by polycondensing a phenol and an aldehyde under an acid catalyst. Examples of such phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-cresol
-Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol , P-phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, 2-methylhydroquinone, phloroglucinol, pyrogallol, 1-naphthol, 2-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like. be able to.

Among these, phenol, o-cresol, m-cresol, p-cresol, m-ethylphenol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol 2,
Preferred are 3,5-trimethylphenol, hydroquinone, resorcinol, 2-methylresorcinol, 2-methylhydroquinone, phloroglicinol, pyrogallol, bisphenol A and the like. These phenols are used alone or in combination of two or more.

The aldehydes include, for example, formaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α
-Phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde , P
-Nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural and the like are used. Particularly, formaldehyde can be suitably used.

Here, as a formaldehyde generating source, formalin, trioxane, paraformaldehyde, methyl hemiformal, ethyl hemiformal, propyl hemiformal, butyl hemiformal, phenyl hemiformal, and the like can be mentioned. Particularly, formalin and butyl hemiformal can be mentioned. Formal can be suitably used. These aldehydes are used alone or in combination of two or more. The amount of the aldehyde used is preferably 0.7 to 3 mol per 1 mol of the phenol.

Examples of the acid catalyst used for the polycondensation include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-toluenesulfonic acid and the like. The amount of these acid catalysts used is
Usually, 1 × 10 ^{−4 to} 5 × 1 per mole of phenols
0 ^-1 mol.

In the polycondensation, water is usually used as a reaction medium. If the phenol used in the polycondensation does not dissolve in the aqueous solution of the aldehyde and becomes inhomogeneous from the beginning of the reaction, a hydrophilic medium is used as the reaction medium. Aprotic solvents can also be used. Examples of these hydrophilic solvents include methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane and the like. The amount of the reaction medium is usually 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

The polystyrene-equivalent weight average molecular weight (hereinafter, referred to as [Mw]) of the novolak resin used in the present invention is preferably from 2,000 to 25,000, more preferably from 3,500 to 15,000. Mw is 2,000
If it is less than 0, developability, sensitivity and the like are liable to be deteriorated.
If it exceeds 0, developability, resolution and the like tend to deteriorate.
The novolak resins are used alone or in combination of two or more.

The polyhydroxystyrene resin used in the present invention is a polymer containing a structural unit corresponding to a structure in which a polymerizable double bond of hydroxystyrene is cleaved.

Here, the hydroxystyrenes include:
For example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 3-chloro-4-hydroxystyrene, 4-chloro-3-hydroxystyrene,
2-chloro-3-hydroxystyrene, 4-bromo-3
-Hydroxystyrene, 3-ethyl-4-hydroxystyrene, 3-propyl-4-hydroxystyrene, 3-
t-butyl-4-hydroxystyrene, 3-phenyl-
4-hydroxystyrene, 3-naphthyl-4-hydroxystyrene, 3-benzyl-4-hydroxystyrene,
Styryl-4-hydroxystyrene, 3-vinyl-4-
Hydroxystyrene, 3-propenyl-4-hydroxystyrene, 3-cumyl-4-hydroxystyrene, 2-
Methyl-4-hydroxystyrene, 2,6-dimethyl-
4-hydroxystyrene, p-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, o-
Hydroxy-α-methylstyrene and the like.

As a method for obtaining the above-mentioned polyhydroxystyrene resin, a method of polymerizing by radical polymerization, cationic polymerization, anionic polymerization, thermal polymerization or the like, or a method of Macrom
olecules, 1989, 22 , 509-516, etc., after protecting the phenolic hydroxyl group of the corresponding monomer with a t-butyl group, an acetyl group, a t-butoxycarbonyl group, a trialkylsilyl group, and the like, and then polymerizing. And a method obtained by removing a protecting group by hydrolysis. The latter method is preferable.

The polyhydroxystyrene resin may be, for example, acrylic acid, methyl acrylate,
Ethyl acrylate, glycidyl acrylate, propyl acrylate, methoxyvinyl, t-butoxyvinyl, styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, maleic anhydride, vinyl acetate, vinylpyridine, vinylpyrrolidone, acrylonitrile, etc. The structural unit in which the polymerizable double bond is cleaved is, for example, 1 of all the structural units.
It may contain about 0% or less.

The Mw of the polyhydroxystyrene resin used in the present invention is preferably 5,000 to 300,0.
00, more preferably 10,000 to 150,000. When Mw is less than 5,000, heat resistance is likely to deteriorate,
If it exceeds 300,000, developability, resolution, coatability and the like tend to deteriorate. Polyhydroxystyrene resin is
They may be used alone or in combination of two or more.

Compound (a) The compound (a) of the present invention is a compound having a structure represented by the aforementioned structural formula (1).

The alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ⁸ in the structural formula (1) includes a methyl group, an ethyl group,
n-propyl group, i-propyl group, t-butyl group, etc.
Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and a t-
Butoxy group and the like.

Further, the carbon number of R ⁹ and R ¹⁰ is 1 to
Examples of the alkyl group 4 include the same as those exemplified for R ^{1 to} R ⁸ .

In the structural formula (1), preferred R
^{1 to} R ⁸ are a methyl group, an ethyl group, an i-propyl group, a t-
A is preferably -CR ⁹ R ^10- , and preferred R ⁹ and R ¹⁰ are a hydrogen atom, a methyl group, i
-Propyl group and cyclohexylidene group.

Compound (a) is characterized in that the phenolic hydroxyl group has an intramolecular hydrogen bond and has alkali solubility. This structural feature suppresses the swelling of the resist pattern.
It has the property that it is hard to cause. In addition, the compound (a) is preferably a KrF excimer laser (248n
m) is a compound whose light transmittance is higher than that of a novolak resin and which is dropped by irradiation with the radiation source.

The compound (a) can be obtained, for example, by reacting a phenol with a methylol compound of bisphenol obtained by reacting a bisphenol with formaldehyde with a basic catalyst.

As the bisphenols, preferred are, for example, bisphenol A (4,4 '-(1-
(Methylethylidene) bisphenol), bisphenol F (4,4'-methylenebisphenol), bisphenol E (4,4'-ethylidenebisphenol), bisphenol Z (4,4'-cyclohexylidenebisphenol), bisphenol S (4,4 '-Sulfonyldiphenol), 4,4'-(1,3-dimethylbutylidene) bisphenol, 4,4 '-(1-phenylethylidene) bisphenol, 4,4'-(2-methylpropylidene) bisphenol, 4,4'-oxybisphenol, 4,4'-propanediylbisphenol,
4 '-(2-methylpropylidene) bisphenol,
4,4 ′-(3-methylbutylidene) bisphenol,
4,4 ′-(phenylmethylene) bisphenol and the like. As the phenol, a monovalent phenol is preferable, and a phenol having a substituent at the 5-position and / or 2-position is more preferable.

Examples of such phenols include phenol, p-cresol, p-ethylphenol,
p-propylphenol, p-butylphenol, 2,
4-xylenol, 2-methyl-4-ethylphenol, 2-methyl-4-butylphenol, 4-butyl-
2-methylphenol, p-methoxyphenol, p-
Ethoxyphenol, p-propoxyphenol, p-
Butoxyphenol and the like.

As such a compound (a), for example, 2,2 ′, 6,6′-tetrakis (2-hydroxybenzyl) bisphenol A, 2,2 ′, 6,6′-tetrakis (2-hydroxy- 5-methylbenzyl) bisphenol A, 2,2 ′, 6,6′-tetrakis (3,5-dimethyl-2-hydroxybenzyl) bisphenol A, 2,2
2 ', 6,6'-tetrakis (2-hydroxy-5-ethylbenzyl) bisphenol A, 2,2', 6,6'-tetrakis (2-hydroxy-5-tert-butylbenzyl) bisphenol A, 2,2 2 ′, 6,6′-tetrakis (2-hydroxybenzyl) bisphenol F,
2 ′, 6,6′-tetrakis (2-hydroxy-5-methylbenzyl) bisphenol F, 2,2 ′, 6,6′-tetrakis (3,5-dimethyl-2-hydroxybenzyl) bisphenol F, 2 ′, 6,6′-tetrakis (2-hydroxy-5-ethylbenzyl) bisphenol F, 2,2 ′, 6,6′-tetrakis (2-hydroxy-5-tert-butylbenzyl) bisphenol F,
2 ', 6,6'-tetrakis (2-hydroxybenzyl)
Bisphenol C, 2,2 ', 6,6'-tetrakis (2
-Hydroxy-5-methylbenzyl) bisphenol Z, 2,2 ', 6,6'-tetrakis (3,5-dimethyl-
2-hydroxybenzyl) bisphenol Z, 2,2 ′,
6,6′-tetrakis (2-hydroxy-5-ethylbenzyl) bisphenol Z, 2,2 ′, 6,6′-tetrakis (2-hydroxy-5-tert-butylbenzyl) bisphenol Z, 2,2 ′, 6,6'-tetrakis (2-
(Hydroxybenzyl) bisphenol S, 2,2 ′, 6,
6'-tetrakis (2-hydroxy-5-methylbenzyl) bisphenol S, 2,2 ', 6,6'-tetrakis (3,5-dimethyl-2-hydroxybenzyl) bisphenol S, 2,2', 6, 6'-tetrakis (2-hydroxy-5-ethylbenzyl) bisphenol S, 2,
2 ', 6,6'-tetrakis (2-hydroxy-5-tert
-Butylbenzyl) bisphenol S, 2,2 ', 6,
6'-tetrakis (2-hydroxybenzyl) bisphenol B, 2,2 ', 6,6'-tetrakis (2-hydroxy-5-methylbenzyl) bisphenol E, 2,2
2 ', 6,6'-tetrakis (3,5-dimethyl-2-hydroxybenzyl) bisphenol E, 2,2', 6,
6′-tetrakis (2-hydroxy-5-ethylbenzyl) bisphenol E, 2,2 ′, 6,6′-tetrakis (2-hydroxy-5-tert-butylbenzyl) bisphenol E,

Bis [3,5-bis (2'-hydroxybenzyl) -4-hydroxyphenyl] phenylmethane,
Bis [3,5-bis (2'-hydroxy-5'-methylbenzyl) -4-hydroxyphenyl] phenylmethane, bis [3,5-bis (5'-tert-butyl-
2'-hydroxybenzyl) -4-hydroxyphenyl] phenylmethane, bis [3,5-bis (3 ', 5'-
Dimethyl-2'-hydroxybenzyl) -4-hydroxyphenyl] phenylmethane, 1,1-bis [3,5-bis (2'-hydroxybenzyl) -4-hydroxyphenyl] -1-phenylethane, 1,1 -Bis [3,5-bis (2'-hydroxy-5'-methylbenzyl) -4-
Hydroxyphenyl] -1-phenylethane, bis [3,5-bis (5′-tert-butyl-2′-hydroxybenzyl) -4-hydroxyphenyl] -1-phenylethane, 1,1-bis [3, 5-bis (3 ', 5'
-Dimethyl-2'-hydroxybenzyl) -4-hydroxyphenyl] -1-phenylethane and the like.

Of these, 2,2 ', 6,6'-tetrakis (2-hydroxy-5-methylbenzyl) bisphenol A, 2,2', 6,6'-tetrakis (3,5-dimethyl-2 -Hydroxybenzyl) bisphenol A,
2,2 ′, 6,6′-tetrakis (5-tert-butyl-2-hydroxybenzyl) bisphenol A,
2 ′, 6,6′-tetrakis (2-hydroxy-5-methylbenzyl) bisphenol F, 2,2 ′, 6,6′-tetrakis (5-tert-butyl-2-hydroxybenzyl) bisphenol F, 2 ′, 6,6′-tetrakis (3,5-dimethyl-2-hydroxybenzyl) bisphenol F, 2,2 ′, 6,6′-tetrakis (2-hydroxy-5-methylbenzyl) bisphenol S,
2,2 ', 6,6'-tetrakis (2-hydroxy-5-
Methylbenzyl) bisphenol E, 2,2 ', 6,6'
-Tetrakis (2-hydroxy-5-ethylbenzyl)
Bisphenol Z, bis [3,5-bis (2'-hydroxy-5'-methylbenzyl) -4-hydroxyphenyl] phenylmethane, 1,1-bis [3,5-bis (2 '
-Hydroxy-5'-methylbenzyl) -4-hydroxyphenyl] -1-phenylethane is preferred.

The compounding amount of the compound (a) is preferably 2 to 50 parts by weight, more preferably 3 to 30 parts by weight, particularly preferably 5 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble resin. If the amount is less than 2 parts by weight, it is difficult to obtain a sufficient swelling suppressing effect. In addition, the developability of the non-irradiated portion exceeding 50 parts by weight deteriorates, and it becomes difficult to form a pattern. The compound (a) is used alone or in combination of two or more.

Various Compounding Agents The compound of the present invention may contain various compounding agents such as dissolution inhibitors, sensitizers, surfactants, dissolution accelerators, and acid diffusion controllers. The dissolution inhibitor is a compound used for the purpose of lowering the alkali solubility and making it possible to form a pattern when the alkali solubility of the alkali-soluble resin is too high, and as such, baking, irradiation, development, etc. Is hardly chemically changed by the above process.

Examples of such a compound include aromatic compounds such as naphthalene, phenanthrene and anthracene; ketones such as acetophenone, benzophenone and phenylnaphthyl ketone;
And sulfones such as diphenyl sulfone and dinaphthyl sulfone.

The amount of such a dissolution inhibitor is usually not more than 50 parts by weight, preferably not more than 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin.

The sensitizer absorbs the energy of the radiation and transfers the energy to the acid generator when the sensitivity of the composition is low or when the photosensitivity to the radiation irradiated by the acid generator is low. It is blended to generate an acid by transmission. Examples of such a sensitizer include acetone, benzene, acetophenone, naphthalene, biacetyl, eosin, rose bengal, pyrene, anthracene, and phenothiazine. The compounding amount of such a sensitizer is usually 50 parts by weight or less, preferably 30 parts by weight or less based on 100 parts by weight of the alkali-soluble resin.

The surfactant is blended for improving the coating property and the developing property of the composition. Examples of such a surfactant include polyoxyethylene lauryl ether and polyoxyethylene oleyl ether. Surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and EFTOP EF3
01, EF303, EF352 (trade name, manufactured by Shin-Akita Kasei Co., Ltd.), Megafax F171, F172, F
173 (trade name, manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 (trade name, manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon
S-382, SC-101, SC-102, SC-10
3. Fluorosurfactants such as SC-104, SC-105, SC-106 (trade name, manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); acrylic acid Or methacrylic acid (co) polymer polyflow No. 75, No. 95 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amounts of these surfactants are as follows.
It is usually 2 parts by weight or less per 0 parts by weight.

The purpose of the dissolution accelerator is to promote the alkali solubility of the composition, and examples thereof include a low molecular weight phenol compound. As the low molecular weight phenol compound used here, a phenol compound having about 2 to 6 benzene rings is preferably used. The amount of such a dissolution promoter is usually 50 parts by weight or less based on 100 parts by weight of the alkali-soluble resin.

The purpose of the acid diffusion control agent is to control the diffusion of the acid generated by the irradiation of radiation, and to improve the pattern shape, the dimensional fidelity according to the mask dimensions, and the like.

As such an acid diffusion controlling agent, a nitrogen-containing basic compound can be preferably used. For example, ammonia, triethylamine, tripropylamine, tributylamine, aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline,
4-methylaniline, 4-nitroaniline, 1-naphthylamine, 2-naphthylamine, diphenylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, pyrrolidine, piperidine, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, Thiabendazole, pyridine, 2-methylpyridine, 4-ethylpyridine, 1-methyl-4-
Phenylpyridine, 2- (1-ethylpropyl) pyridine, nicotinamide, dibenzoylthiamine, riboflavin tetrabutyrate, 4,4′-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-
Bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane,
2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2-
(4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl)-
1-methylethyl] benzene,

Dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly {[6- (1,1,3,3-
(Tetramethylbutyl) imino-1,3,5-triazine-
2,4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidiyl) imino] hexamethylene [(2,2,6,
6-tetramethyl-4-piperidiyl) imino]｝, 2
Bis (1,2,2,6,6-)-(3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate
Pentamethyl-4-piperidyl) and the like.

The acid diffusion controllers may be used alone or in combination of two or more. The amount of the acid diffusion controller to be used is generally 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the alkali-soluble resin. If the amount is too small, the pattern shape and dimensional fidelity tend to deteriorate, and if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the non-irradiated part tends to deteriorate.

Preparation of Composition and Pattern Formation The composition of the present invention is prepared by mixing the above-mentioned alkali-soluble resin, acid generator, cross-linking agent and various compounding agents, for example, so that the solid content concentration becomes 20 to 40% by weight. Dissolved in a solvent,
It is prepared by filtering through 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, and methyl cellosolve acetate.
G, ethyl cellosolve acetate, diethylene glyco-
Monomethyl ether, diethylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-
Heptanone, ethyl 2-hydroxypropionate, 2-
Ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-
Methyl 3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl acetate, butyl acetate, ethyl pyruvate and the like can be used. These organic solvents are used alone or in combination of two or more.

Further, N-methylformamide, N, N
-Dimethylformamide, N-methylformanilide,
N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1
-Octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate
A high-boiling solvent such as g.

The composition of the present invention is applied to, for example, a silicon wafer or a wafer coated with aluminum or the like by spin coating, flow coating, roll coating or the like to form a resist film, and a predetermined mask is formed. Irradiating the resist film with radiation through the pattern;
Post-baking is carried out at a temperature of ° C., followed by development with a developer comprising an alkali-soluble resin, followed by rinsing.

[0117]

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

Mw: GPC column (G2 manufactured by Tosoh Corporation)
000H _XL two, G3000H _XL one, G4000
_H.L.H. 1), gel permeation chromatography using monodisperse polystyrene as a standard under the analysis conditions of a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C.

Optimum exposure dose: A resist film is formed, irradiated with radiation through a pattern mask, post-baked, developed with a developing solution consisting of a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, and developed with water. Rinse,
Dry to form a resist pattern on the wafer,
0.6 μm line and space pattern (1 L
1S) to obtain a 1: 1 width of radiation (hereinafter referred to as “optimal exposure amount”). Irradiation was performed with a 248 nm KrF laser using MBK-400TL-N manufactured by Admon Science Co., Ltd.

Resolution: The size of the smallest resist pattern resolved at the time of irradiation with the optimal exposure time was measured. Developability: The scum of the unirradiated portion, the degree of undeveloped portion, the swelling and meandering of the pattern were examined.

Synthesis Example 1 176 g (1.0 mol) of p-tert-butoxystyrene, 8.2 g (0.05 mol) of azobisisobutyronitrile and 4.0 g (0.02 mol) of dodecylmercaptan were added to 100 ml of dioxane. , And reacted for 10 hours while maintaining the internal temperature at 75 ° C. to remove unreacted substances.
tert-butoxystyrene). Subsequently, this poly (p-tert-butoxystyrene) was hydrolyzed with an acid to obtain poly (p-hydroxystyrene) having Mw = 8,900. This resin is referred to as a resin (A1).

Synthesis Example 2 176 g of dried p-tert-butoxystyrene
(1.0 mol) was dissolved in 1,000 ml of dry toluene, and 1M of hydrogen iodide was added under a dry nitrogen atmosphere.
4 ml of n-hexane solution and then 0.5 ml of zinc iodide
8 ml of a M diethyl ether solution were added. afterwards,
The reaction was carried out for 4 hours while keeping the internal temperature at 25 ° C. or lower, the reaction was stopped by adding a methanol solution containing a small amount of aqueous ammonia, and unreacted substances were removed to obtain poly (p-tert-butoxystyrene). Was. Subsequently, the poly (p-te
rt-butoxystyrene) is hydrolyzed with an acid to give Mw
= 7,200 poly (p-hydroxystyrene) was obtained. This resin is referred to as a resin (A2).

Synthesis Example 3 22.8 g (0.1 mol) of bisphenol A and 28 g (0.21 mol) of a 30% by weight aqueous sodium hydroxide solution were mixed and cooled to room temperature. 34 g of 37% by weight formalin (0.42 mol of formaldehyde) was added to the mixture, and the mixture was reacted at 35 ° C. for 4 hours. After the reaction, 30 ml of concentrated hydrochloric acid was carefully added while cooling so that the internal temperature did not exceed 40 ° C., and 130 g (1.2 mol) of p-cresol was further added. Allowed to react for hours.

Thereafter, the reaction mixture was washed several times with water to remove sodium chloride and hydrochloric acid, and distilled under reduced pressure to remove excess p-
The cresol was distilled off to obtain a brown resin residue. This residue was heated under reflux with 100 ml of toluene for several minutes, and then cooled to room temperature to produce a white precipitate. The precipitate was filtered off and washed several times with toluene to give a white 2,2.
2 ′, 6,6′-Tetrakis [(2-hydroxy-5-methylphenyl) methyl] bisphenol A was obtained (hereinafter referred to as “compound (a1)”).

Synthesis Example 4 In the same manner as in Synthesis Example 3, 24.2 g of bisphenol B (0.2%
1 mol), 34 g of 37% by weight formalin (0.42 mol of formaldehyde) and 147 g of 2,4-xylenol
(1.2 mol), purified, and white 2,2 ′, 6,
6′-Tetrakis [(3,5-dimethyl-2-hydroxydiphenyl) methyl] bisphenol B was obtained (hereinafter referred to as “compound (a2)”).

Examples 1 to 4 and Comparative Example 1 A polyhydroxystyrene resin having a composition shown in Table 1 (parts are parts by weight), a crosslinking agent, a compound (a), an acid generator and a solvent were mixed. , A uniform solution, and a pore size of 0.
The solution was filtered through a 2 μm membrane filter to prepare a composition solution. After applying the above composition solution on a silicon wafer with a spinner, it is pre-baked at 100 ° C. for 100 seconds to form a resist film having a thickness of 1.2 μm, and is irradiated with radiation through a pattern mask. Post bake was performed for 90 seconds. Next, the film was developed with a developer at 23 ° C. for 1 minute by an immersion method, and rinsed with ultrapure water for 30 seconds. Table 1 shows the evaluation results of the resist. In addition, the acid generator and the solvent in Table 1 are as follows.

[0127]

[Table 1]

Acid generator (B1): triphenylsulfonium triflate (B2): diphenyliodonium triflate (B3): 2-phenyl-4,6-dichloromethyl-1,
3,5-triazine crosslinking agent (C1): hexamethoxymethylmelamine (C2): α, α′-dimethoxy-p-xylene (C3): α, α′-bis (2,6-dimethoxymethyl-)
4-methylphenoxy) -p-xylene (C4): trioxane Solvent (α): ethylene glycol monoethyl ether acetate (β): methyl 3-methoxypropionate (γ): ethyl 2-hydroxypropionate

[0129]

The negative-type radiation-sensitive resin composition of the present invention is excellent in sensitivity, developability, resolution, etc., as a negative resist having no swelling of the pattern during development and no meandering of the pattern.
Especially ultraviolet, far ultraviolet, X-ray, electron beam, molecular beam, γ-ray,
It can be suitably used as a negative resist for producing an integrated circuit which is sensitive to radiation such as synchrotron radiation and proton beam.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takao Miura 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-4-122938 (JP, A) JP-A 4-251849 (JP, A) JP-A-62-38448 (JP, A) JP-A-4-291261 (JP, A) JP-A-57-111529 (JP, A) (58) Fields investigated (Int. Cl. ^7, DB name) G03F 7/038 G03F 7/004 H01L 21/027

Claims (1)

(57) [Claims] (1) a compound that generates an acid upon irradiation with radiation, (2) a crosslinking agent that undergoes a crosslinking reaction in the presence of an acid, (3)
An alkali-soluble resin, and (4) the following structural formula (1): A negative radiation-sensitive resin composition comprising a phenolic compound represented by the formula: