JP2000122283A - Resist material, photosensitive resin composition using the material, and method for using the composition for production of semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce a rechety pattern in the case of forming a fine pattern by (co)polymerizing monomers containing specified compds. to form a pattern. SOLUTION: A pattern is formed by (co)polymn. of monomers containing at least one kind of compd. selected form the group consisting of compds. expressed by the formula. In the formula, R1 is hydrogen atom, a 1-10C alkoxy group, carboxyl group, halogen atom, -SR3 or 6-20C aromatic group, wherein R3 is hydrogen atom or a 1-5C hydrocarbon group, A is CH2=C(R2)-COO-(CH2)n-, CH2=C(R2)-O-CO-(CH2)n-, CH2=CH-O-(CH2)n or the like, wherein R2 is hydrogen atom, a 1-4C hydrocarbon group, -CN or halogen atom, and n is an integer 1 to 10. Or, the pattern is formed by (co)polymn. of one kind of the compds. expressed by the formula by 1 to 100 mol% and monomers copolymerizable with the compds. of the formula by 0 to 99 mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist for use in forming a fine pattern of a semiconductor device such as an VLSI, for example, a radiation-sensitive resist or a pattern forming material such as a printed board. material,
The present invention relates to a photosensitive resin composition using the material and a method of using the photosensitive resin composition for manufacturing a semiconductor device.

[0002]

2. Description of the Related Art With the demand for higher integration of semiconductor devices, development of microfabrication technology has been advanced. In order to realize formation of a fine pattern, an exposure method using ultraviolet light, X-ray, electron beam, or the like has been proposed. By using these exposure methods, we aim to form a pattern at the 0.2 micron level.

Conventionally, as a resist for photolithography, a resist composed of a novolak resin and naphthoquinonediazide, or a resist composed of a polymer containing tertiary (hereinafter referred to as tert-) butoxycarbonyloxystyrene as a polymerization component and an acid generator has been used. Used.
In the resist, a polymer compound such as a novolak resin or a polystyrene derivative is used as a base material. These high molecular compounds are obtained by polymerizing a low molecular weight compound called a monomer, and have a linear structure in which a monomer or a unit reacted with the monomer is repeated.

However, in a resist using a conventionally used polymer compound as a base material, since the base material molecules are large, as the size of the target fine pattern becomes smaller, the edge portion of the pattern becomes smaller. There is a problem that the rattling is conspicuous and a good pattern cannot be formed.

[0005] As a study focusing on this problem, the Japan Journal of Applied Physics (Japa
n Journal of Applied Physics, Vol. 32, p. 6065 (published in 1993), studies have been made to solve the above problem by reducing the molecular weight of the resin as a base material or adjusting the molecular weight distribution. .

[0006]

In the above-mentioned method, although the play of the pattern edge is slightly improved, the entanglement between the linear polymer compounds is increased by adjusting only the molecular weight and the molecular weight distribution of the resin. , The problem has not yet been completely solved.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a resist material capable of reducing pattern rattling in a fine pattern, a photosensitive resin composition using the material, and the composition. It is an object of the present invention to develop a method of using a product for manufacturing a semiconductor device.

[0008]

According to the present invention, a compound represented by the general formula (I):

[0009]

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Wherein R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a carboxyl group, a halogen atom, —SR ³ , an aromatic group having 6 to 20 carbon atoms. Wherein R ³ is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, and A is CH ₂ ＣC (R ² ) —COO— (C
_{H 2) n -, CH 2} = C (R 2) -O-CO- (CH 2)
_{n -, CH 2 = CH-} O- (CH 2) n -, CH 2 = C
(R ² ) —COO— (CH ₂ ) _n —O—, wherein R ² is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, —CN, a halogen atom, and n is an integer of 1 to 10. Compound represented by the general formula (II):

[0011]

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(Wherein R ¹ is the same as above, B is CH ₂ =
^{C (R 2) -COO-, CH} 2 = C (R 2) -COO-
_{(CH 2) n-, CH 2} = C (R 2) -O-CO- (C
_{H 2) n-, CH 2 =} CH-O-CH 2 -, CH 2 = CH
-, M is an integer of 1 to 10, provided that R ² and n are the same as described above), a compound represented by the general formula (III):

[0013]

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Wherein R ¹ , R ² , and n are the same as those described above, and a compound represented by the general formula (IV):

[0015]

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(Wherein R ¹ , R ² , and n are the same as those described above).
The present invention relates to a material for an alkali-soluble resist obtained by (co) polymerizing a monomer containing a seed.

According to a second aspect of the present invention, at least one of the compounds represented by the general formulas (I) to (IV) is 1 to 100 mol% and the compound represented by the general formulas (I) to (IV). 2. The material for an alkali-soluble resist according to claim 1, which is obtained by (co) polymerizing 0 to 99 mol% of a monomer having copolymerizability.

According to a third aspect of the present invention, at least one of the compounds represented by the general formulas (I) to (IV) is 20 to 80 mol% and the compound represented by the general formulas (I) to (IV). And a monomer having a copolymerizability of 20 to 80 mol%
2. The material for an alkali-soluble resist according to claim 1, which is obtained by copolymerizing the following.

According to a fourth aspect of the present invention, there is provided at least one compound selected from the group consisting of compounds represented by the general formulas (I) to (IV) wherein a hydroxyl group and a carboxyl group are substituted by an acid labile group. The present invention relates to an alkali-insoluble resist material obtained by (co) polymerizing a monomer containing

According to a fifth aspect of the present invention, at least one compound selected from the group consisting of compounds represented by the general formulas (I) to (IV) in which a hydroxyl group and a carboxyl group are substituted with an acid labile group is 1 to 100 moles. % And general formulas (I) to (IV)
5. The alkali-insoluble compound according to claim 4, which is obtained by (co) polymerizing a compound having a hydroxyl group and a carboxyl group substituted by an acid labile group with a monomer having copolymerizability of 0 to 99 mol%. It relates to a resist material.

According to a sixth aspect of the present invention, at least one of the compounds represented by the general formulas (I) to (IV), in which the hydroxyl group and the carboxyl group are substituted with an acid labile group, is contained in an amount of 20 to 80 mol. % And general formulas (I) to (IV)
5. The compound for an alkali-insoluble resist according to claim 4, which is obtained by copolymerizing a compound in which a hydroxyl group and a carboxyl group of the compound represented by the formula are substituted with an acid labile group and 20 to 80 mol% of a copolymerizable monomer. It is about materials.

According to a seventh aspect of the present invention, at least one of the compounds represented by the general formulas (I) to (IV) is 10 to 90 mol% and the compound represented by the general formulas (I) to (IV). And an alkali-insoluble resist material obtained by copolymerizing 10 to 90 mol% of a monomer having an acid labile group which is copolymerizable with an acid and decomposed by an acid to generate a phenolic hydroxyl group or a carboxyl group. It is.

Claim 8 according to the present invention is claim 1,
The material for an alkali-soluble resist according to 2 or 3, the material for an alkali-insoluble resist according to claim 4, 5, 6 or 7, and an acid generator, wherein the material for an alkali-soluble resist / the material for an alkali-insoluble resist is: The present invention relates to a photosensitive resin composition having a weight ratio of 0/100 to 90/10.

According to a ninth aspect of the present invention, the ratio of the resist material / acid generator is 90/10 to 99.9 / weight ratio.
The photosensitive resin composition according to claim 8, which is 0.1.

According to a tenth aspect of the present invention, in manufacturing a semiconductor device, a film is provided on a semiconductor substrate using a photosensitive resin composition, and light or radiation is patterned on the photosensitive resin composition film. The present invention relates to a method of using the photosensitive resin composition according to claim 8 or 9 for manufacturing a semiconductor device in which the photosensitive resin composition film after the exposure is exposed and then developed.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION There are two types of resist materials of the present invention, one for alkali-soluble resists and one for non-alkaline resists.

The above-mentioned alkali-soluble resist material and the above-mentioned alkali-insoluble resist material use a specific compound described below as a monomer. The effect that rattling is reduced is obtained. This effect is considered to be due to self-rearrangement of the resist material.

The alkali-soluble resist material has at least one of a phenolic hydroxyl group and a carboxyl group in the molecule, and is dissolved by washing with an alkaline solution. A material having a thickness of 5000 angstroms that can be dissolved in 60 seconds or less when washed with an aqueous solution of .38% by weight of tetramethylammonium hydroxide.

The alkali-soluble resist material is not used alone in the photosensitive resin composition,
It is used in combination with an alkali-insoluble resist material described later. A photosensitive resin composition is produced using a mixture of an alkali-soluble resist material and an alkali-insoluble resist material, and when used as a resist, before exposure, the one that was alkali-insoluble as a whole resist, The exposure converts the alkali-insoluble resist material into an alkali-soluble resist material, so that the exposed portion becomes alkali-soluble as a whole resist. At this time, due to the presence of the alkali-soluble resist material, the difference in solubility between the exposed portion and the non-exposed portion in an alkali solution increases, and a resist pattern is obtained. The material for an alkali-soluble resist is used for the purpose described above.

The alkali-soluble resist material is specifically represented by the following general formula (I):

[0031]

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(Wherein, R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a carboxyl group, a halogen atom, —SR ³ , an aromatic group having 6 to 20 carbon atoms. Wherein R ³ is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, and A is CH ₂ ＣC (R ² ) —COO— (C
_{H 2) n -, CH 2} = C (R 2) -O-CO- (CH 2)
_{n -, CH 2 = CH-} O- (CH 2) n -, CH 2 = C
(R ² ) —COO— (CH ₂ ) _n —O—, wherein R ² is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, —CN, a halogen atom, and n is an integer of 1 to 10. Compound represented by the general formula (II):

[0033]

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(Wherein R ¹ is the same as above, B is CH ₂ =
^{C (R 2) -COO-, CH} 2 = C (R 2) -COO-
_{(CH 2) n-, CH 2} = C (R 2) -O-CO- (C
_{H 2) n-, CH 2 =} CH-O-CH 2 -, CH 2 = CH
-, M is an integer of 1 to 10, provided that R ² and n are the same as described above), a compound represented by the general formula (III):

[0035]

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Wherein R ¹ , R ² and n are the same as defined above, and a compound represented by the general formula (IV):

[0037]

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(Wherein R ¹ , R ² , and n are the same as those described above), and a monomer containing at least one selected from the group consisting of compounds represented by the following formula (hereinafter, also referred to as compound group (a)): This is an alkali-soluble resist material obtained by (co) polymerizing a monomer (Z).

The monomer (Z) includes, in addition to the compound belonging to the compound group (a), a monomer copolymerizable with the compound belonging to the compound group (a) (hereinafter, also referred to as monomer (x)). ) May be included.

As the alkali-soluble resist material, at least one compound selected from the compound group (a) is used in an amount of 1 to 100 mol%, from the viewpoints of alkali solubility, reduction of pattern edge wobble, economy, and the like. 20-8
0 mol%, 0 to 99 mol% of monomer (x), and 2
Those obtained by (co) polymerizing 0 to 80 mol% are preferred.

Preferred specific examples of the compounds belonging to the compound group (a) include, for example,

[0042]

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(Hereinafter, also referred to as compound group (c)).

The monomer (x) includes, for example, a group consisting of compounds in which the phenolic hydroxyl group and carboxyl group of the compounds belonging to the compound group (a) are substituted with acid labile groups (hereinafter referred to as compound group (b) ), Hydroxystyrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, p-chlorostyrene, p-bromostyrene, p-
Aromatic vinyl compounds such as iodostyrene, tert-butoxycarbonyloxystyrene, tert-butyloxystyrene, tetrahydropyranyloxystyrene, trimethylsilyloxystyrene, carboxybenzyl vinyl ether, acrylic acid, acrylic acid-ter
t-butyl ester, methacrylic acid, methacrylic acid-t
tert-butyl ester, ethoxyethyl methacrylate, tetrahydropyranyl methacrylate and the like. These may be used alone,
A combination of more than one species may be used. Among these, they belong to the compound group (b) because they can effectively reduce the rattling of the pattern edge.

[0045]

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(Hereinafter, also referred to as compound group (d)),

[0047]

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Compounds such as are preferred.

The acid labile group in the compound belonging to the monomer (x) is effectively decomposed by an acid, and becomes alkali-soluble.

The acid labile groups include, for example, ter
t-butyl ether group, tert-amyl ether group,
Trimethylsilyl ether group, tert-butyldimethylsilyl ether group, tetrahydropyranyl ether group, tetrahydrofuranyl ether group, methoxyethyl ether group, ethoxyethyl ether group, propoxyethyl ether group, butoxyethyl ether group, methoxypropyl ether group, ethoxypropyl ether Group, t
tert-butyl ester group, tert-amyl ester group, trimethylsilyl ester group, tert-butyldimethylsilyl ester group, tetrahydropyranyl ester group, tetrahydrofuranyl ester group, methoxyethyl ester group, ethoxyethyl ester group, propoxyethyl ester group, butoxy Ethyl ester group, methoxypropyl ester group, ethoxypropyl ester group,
tert-butoxycarbonyl ether group, tert-
Examples include, but are not limited to, amyloxycarbonyl ether groups. Of these, tert-
A butyl ester group, a tert-butoxycarbonyl ether group, a tetrahydropyranyl ester group and the like are preferable.

Compounds belonging to the compound group (a) forming the alkali-soluble resist material, alkali-soluble compounds such as 4-hydroxystyrene having copolymerizability with these compounds and alkali-non-soluble compounds such as the compounds belonging to the compound group (b). The proportion of the soluble compound is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and the latter is 0 to 40 mol%, and more preferably 0 to 30 mol%. It is preferable in that a soluble resist material can be obtained.

The ratio of the compound belonging to the compound group (a) and the compound belonging to the compound group (b) forming the alkali-soluble resist material to the other compounds having copolymerizability with them is as follows. 1 to 100 mol%,
Furthermore, 10-100 mol%, the latter is 0-99 mol%,
Further, the content is preferably from 0 to 90 mol% from the viewpoint that a resist material is obtained which has an effect of improving the play of the pattern edge and reducing the play of the pattern in the fine pattern.

The alkali-soluble resist material has a weight average molecular weight of 2,000 to 100,000, and more preferably 50 to 100,000.
It is preferably from 00 to 50,000. When the weight average molecular weight is too small, the alkali insolubility of a portion which should be alkali insoluble during development tends to be insufficient. On the other hand, if it is too large, the viscosity at the time of forming the resist coating film increases, so that it must be used as a low-viscosity composition, and the resolution at the time of development tends to be reduced.

The alkali-soluble resist material includes:
Since a unit from the compound group (a) and further from the compound belonging to the compound group (b) is included, a resist pattern with sharp edges can be obtained.

On the other hand, in the above alkali-insoluble resist material, all or a part of the phenolic hydroxyl group and carboxyl group contained in the molecule are blocked, and the resist material is not dissolved even when washed with an alkaline solution. 23-25 ° C
Is a material having a solubility of 20 nm / sec or less when washed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. When the phenolic hydroxyl group and carboxyl group are blocked by forming an acid labile group, an acid is generated by irradiation with light such as an alkali-insoluble resist material or short-wavelength laser or radiation such as electron beam or X-ray. When a photosensitive resin composition containing a compound to be prepared (hereinafter, also referred to as an acid generator) is produced and used as a resist, by exposure, an alkali-insoluble resist material is converted into an alkali-soluble resist material,
The exposed portion becomes alkali-soluble and is developed to obtain a resist pattern. As described above, the above-mentioned alkali-soluble resist material may be further added to the photosensitive resin composition to improve the pattern accuracy.

The alkali-insoluble resist material is as follows:
Specifically, an alkali-insoluble resist material obtained by polymerizing a monomer containing one or more kinds selected from the compound group (b) (hereinafter, also referred to as a monomer (Y)), and a compound group (a ) At least one selected from 10 to 90 mol%
And a monomer having an acid labile group which is copolymerizable with the compound group (a) and decomposes with an acid to generate a phenolic hydroxyl group or a carboxyl group (hereinafter also referred to as monomer (x ')) 10 To 90 mol% is a material for an alkali-insoluble resist.

The monomer (Y) includes, in addition to the compound belonging to the compound group (b), a monomer copolymerizable with a compound belonging to the compound group (b) (hereinafter, also referred to as a monomer (y)). ) May be included.

The material for the alkali-insoluble resist is preferably at least one selected from the group of compounds (b) from 1 to 100 mol% from the viewpoints of alkali insolubility, reduction of pattern edge wobble, economy, and the like. Is 5-95
Mol%, especially 20 to 80 mol%, and the monomer (y) 0
~ 99 mol%, more preferably 5-95 mol%, especially 20
(Co) -polymerized with at least one of the compound group (a), from 10 to 90 mol%, and more preferably from 20 to 80 mol%, from the monomer (x ′). 10 to 90 mol% of at least one type, more preferably 20 to
A material for an alkali-insoluble resist obtained by copolymerizing 80 mol% of the compound is preferred.

Preferred examples of the compounds belonging to the compound group (b) include, for example, compounds belonging to the compound group (d).

Examples of the monomer (y) include compounds belonging to the compound group (a), hydroxystyrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, p-chlorostyrene, p-
Bromostyrene, p-iodostyrene, tert-butoxycarbonyloxystyrene, tert-butyloxystyrene, tetrahydropyranyloxystyrene, trimethylsilyloxystyrene, aromatic vinyl compounds such as carboxybenzyl vinyl ether, acrylic acid, acrylic acid-tert- Examples thereof include butyl ester, methacrylic acid, tert-butyl methacrylate, ethoxyethyl methacrylate, and tetrahydropyranyl methacrylate. These may be used alone or in combination of two or more. Among them, compounds belonging to the compound group (c) from the viewpoint that the rattling of the pattern edge can be effectively reduced,

[0061]

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And the like.

Examples of the monomer (x ') include compounds belonging to the compound group (b) and those in which the phenolic hydroxyl group or carboxyl group of the aromatic vinyl compound is substituted with an acid labile group. Can be These may be used alone or in combination of two or more. Of these, tert-butoxycarbonyloxystyrene is preferred from the viewpoint that a resist material having excellent performance can be obtained.

The phenolic hydroxyl group and carboxyl group of the compounds belonging to the compound group (b) forming the alkali-insoluble resist material and the aromatic vinyl compound copolymerizable therewith are substituted with acid labile groups. The ratio of the alkali-insoluble compound such as the compound and the alkali-soluble compound such as the compound belonging to the compound group (a) or 4-hydroxystyrene is 10 to 100 mol%, more preferably 20 to 80 mol%, The latter is preferably from 0 to 90 mol%, more preferably from 20 to 80 mol%, from the viewpoint that a resist material having alkali insolubility suitable as a resist material is obtained.

The ratio of the compound belonging to the compound group (a) and the compound belonging to the compound group (b) forming the alkali-insoluble resist material to the other compound having copolymerizability with these compounds is the former. Is 1 to 100 mol%, furthermore, 10 to 100 mol%, and the latter is 0 to 99 mol%, furthermore, the rattling of the pattern edge is improved, It is preferable in that a resist material having an effect of reducing rattling can be obtained.

The weight-average molecular weight of the alkali-insoluble resist material is 2,000 to 100,000, preferably 5 to 100,000.
It is preferably from 000 to 50,000. When the weight average molecular weight is too small, the alkali insolubility of a portion which should be alkali insoluble during development tends to be insufficient. On the other hand, if it is too large, the viscosity at the time of forming the resist coating film increases, so that it must be used as a low-viscosity composition, and the resolution at the time of development tends to be reduced.

Since the alkali-insoluble resist material contains a unit from a compound belonging to the compound group (a) or the compound group (b), a resist pattern having a sharp edge can be obtained.

As described above, the alkali-soluble resist material and the alkali-insoluble resist material are used as a photosensitive resin composition by being combined with an acid generator.

The above photosensitive resin composition shows alkali insolubility as a whole composition. However, if the proportion of alkali soluble material is too large, it becomes difficult for the whole composition to show alkali insolubility. Material / alkali-insoluble resist material in a weight ratio of 0/100 to 90/10, more preferably 0/100 to 80 /
It is preferably 20.

By forming a coating film from the composition and irradiating it with light or radiation, an acid is generated from the acid generator, and the generated acid decomposes the acid-labile groups in the alkali-insoluble resist material. And converted into alkali-soluble groups such as -OH (phenolic hydroxyl group) and -COOH to become alkali-soluble.

If the amount of the acid generator is too small, a sufficient amount of acid is not generated even when irradiated with light or radiation, and the exposed portion cannot be sufficiently alkali-soluble.
It becomes difficult to perform patterning. On the other hand, if the amount of the acid generator is too large, it is difficult to obtain a uniform composition,
The defective rate of the formed pattern increases. In addition, a large amount of acid is generated by irradiation with light or radiation, which makes it difficult to control the decomposition of acid labile groups other than the exposed portions, and the accuracy of the obtained pattern tends to decrease. In addition, the amount of the acid generator used increases, which is uneconomical.

Specific examples of the acid generator include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate, triphenylsulfonium tosylate, triphenylsulfonium methanesulfonate, and 4-tert-butylphenyldiphenylhexafluoroantimonate. , 4-tert-butylphenyldiphenyl triflate, 4-tert-butylphenyldiphenyltosylate, 4-tert-butylphenyldiphenylmethanesulfonate, tris (4-methylphenyl) sulfonium hexafluoroantimonate, tris (4-methylphenyl) Sulfonium triflate, tris (4-methylphenyl) sulfonium tosylate, tris (4-methylphenyl) sulfonium methanes Phonate, tris (4-methoxyphenyl) sulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium triflate, tris (4-methoxyphenyl) sulfonium tosylate, tris (4-methoxyphenyl) sulfonium methanesulfonate, Diphenyliodonium hexafluoroantimonate, diphenyliodonium triflate, diphenyliodonium tosylate, diphenyliodonium methanesulfonate, triphenyliodonium tosylate, 4,4'-di-tert-
Butyldiphenyliodonium hexafluoroantimonate, 4,4'-di-tert-butyldiphenyliodonium triflate, 4,4'-di-tert-butyldiphenyliodonium tosylate, 4,4'-di-tert-butyldiphenyliodonium Methanesulfonate, 4,4'-dimethyldiphenyliodonium hexafluoroantimonate, 4,4'-dimethyldiphenyliodonium triflate, 4,4'-dimethyldiphenyliodonium tosylate, 4,4'-dimethyldiphenyliodonium methanesulfonate, ,
3'-dinitrodiphenyliodonium hexafluoroantimonate, 3,3'-dinitrodiphenyliodonium triflate, 3,3'-dinitrodiphenyliodonium tosylate, 3,3'-dinitrodiphenyliodonium methanesulfonate, naphthylcarbonylmethyltetrahydrothiophenyl Hexafluoroantimonate, naphthylcarbonylmethyltetrahydrothiophenyl triflate, naphthylcarbonylmethyltetrahydrothiophenyltosylate, naphthylcarbonylmethyltetrahydrothiophenylmethanesulfonate,
Dimethylhydroxynaphthyl hexafluoroantimonate, dimethylhydroxynaphthyl triflate, dimethylhydroxynaphthyl tosylate, dimethylhydroxynaphthyl methanesulfonate, trifluoromethanesulfonic acid ester of hydroxysuccinimide, trimethanesulfonic acid ester of hydroxysuccinimide,
Hydroxysuccinimide toluenesulfonic acid ester, hydroxycyclohexanedicarboxylic acid imide trifluoromethanesulfonic acid ester, hydroxycyclohexanedicarboxylic acid imide trimethanesulfonic acid ester, hydroxycyclohexanedicarboxylic acid imide toluenesulfonic acid ester, hydroxynorbornene dicarboxylic acid imide Trifluoromethanesulfonic acid ester, hydroxynorbornene dicarboxylic acid imide trimethanesulfonic acid ester, hydroxynorbornene dicarboxylic acid imide toluenesulfonic acid ester, and the like. These may be used alone,
Two or more kinds may be used in combination. Of these, triphenylsulfonium triflate, diphenyliodonium tosylate, diphenyliodonium triflate, and triphenyliodonium tosylate are preferred from the viewpoint of easy availability and high quantum efficiency.

In the photosensitive resin composition, the weight ratio of resist material / acid generator is 90/10 to 99.9 / 0.9.
1, more preferably 95/5 to 99.5 / 0.5. If the resist material exceeds 99.9% by weight, patterning tends to be difficult to perform,
If the content is less than 90.0% by weight, it is difficult to obtain uniform compatibility, so that a defect in a formed pattern is likely to occur. When the amount of the acid generator is less than 0.1% by weight, a good pattern cannot be formed, and
If the content exceeds 0% by weight, it becomes difficult to obtain uniform compatibility, so that a defect in a formed pattern is likely to occur.

In the manufacture of a semiconductor device, the photosensitive resin composition as described above is provided with a film of the photosensitive resin composition on a semiconductor substrate such as a silicon wafer, and the film is irradiated with a single-wavelength laser beam or the like. Pattern exposure to radiation such as light or electron beam, X-ray, the exposed photosensitive resin composition film,
For example, it is used in a method of manufacturing a semiconductor device by performing development processing with an alkali solution or the like. By using the photosensitive resin composition, it is possible to suppress the rattling of the edge portion of the obtained pattern, so that an ultrafine pattern can be formed.

When providing the film of the photosensitive resin composition, a solvent may be used.
It is common to use a composition concentration of 30% by weight, even 8-20% by weight.

As the solvent, any solvent can be used as long as it can rapidly dissolve the components to be mixed and does not react with them. For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate,
Ethyl ethoxypropionate, ethyl butyrate, 2-heptanone, diglyme, cyclohexanone, cyclopentanone, γ-butyrolactone, isoamyl butyrate, chlorobenzene, dichlorobenzene and the like are common. Preferably, a solvent having a boiling point in the range of 100 to 220 ° C is suitable. If the boiling point is lower than this, unevenness tends to occur when applied, and if the boiling point is higher than this, drying of the solvent is not easy.

When the photosensitive resin composition is coated on a semiconductor substrate to form a film, prebaking is performed, and after irradiation with light or radiation such as X-rays or electron beams,
Perform heating at about 80 to 170 ° C. for 30 seconds to 10 minutes,
Then, the resist can be developed with a developer to form a pattern.

As the developer, an alkaline aqueous solution can be used.

Examples of the alkaline aqueous solution include ammonia, triethylamine, dimethylaminomethanol, monoethanolamine, triethanolamine,
An aqueous solution of a tetraalkylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, choline, or the like, or a mixture of these aqueous solutions can be used.

[0080]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

The resin (1) used in each of the following Examples
In each of (1) to (10), those having a weight average molecular weight of 15,000 were used. Further, the following resins (1) to (10)
The numerical value in the structural formula of (1) is a random copolymerized resin (1).
-Represents the molar ratio of the starting monomer of (10).

Example 1 Resin (1):

[0083]

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(Material for Alkali-Soluble Resist) 4.8
A photosensitive resin composition composed of 5 g and 0.15 g of triphenylsulfonium triflate (acid generator) was dissolved in propylene glycol monomethyl ether acetate to form a 12% by weight solution, and the solution was filtered through a 0.2 micron membrane filter. A photosensitive resin composition solution was prepared.
This solution was applied onto a silicon wafer having enhanced adhesion with hexamethyldisilazane to obtain a 0.5 μm thick pattern forming material film. This film was heated on a hot plate at 100 ° C. for 1 minute. After that, 23-25 ° C, 2.3
6% aqueous solution of 8% tetramethylammonium hydroxide
When the film was immersed for 0 second and the same operation as the development was performed, the film was completely dissolved.

Example 2 A photosensitive resin composition comprising 4.85 g of the resin (2) (material for an alkali-insoluble resist) shown in Table 1 and 0.15 g of triphenylsulfonium triflate (acid generator) was prepared using propylene glycol. It was dissolved in monomethyl ether acetate to make a 12% by weight solution, and the solution was filtered through a 0.2-micron membrane filter to prepare a photosensitive resin composition solution. This solution was applied onto a silicon wafer having enhanced adhesion with hexamethyldisilazane to obtain a 0.5 μm thick pattern forming material film. Acceleration voltage 50k
eV electron beam irradiation of 10 uC / cm ² ,
Heated on a hot plate at 1 ° C. for 1 minute. after that,
Development was carried out with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds. As a result, a 120 nm line and space pattern was resolved with good shape.
The line width of the line and space pattern of this resist was measured at 10 points, and the difference (dimensional uniformity) between the maximum value and the minimum value of the line width was determined to be 10 nm. Table 1 shows the results.

The silicon oxide film could be formed in a pattern of 0.12 μm by processing by the subsequent etching, and a semiconductor device could be manufactured.

Comparative Example 1 In place of the resin (2) of Example 2, a polymer of 4-hydroxystyrene in which 25 mol% of hydroxyl groups were substituted with tert-butoxycarbonyl ether group (material for an alkali-insoluble resist) was used. A pattern was formed in the same manner as in Example 2, and the same measurement was performed. As a result, the resolved line and space pattern is 140 nm
The difference between the maximum value and the minimum value of the line width was 51 nm, and the variation in the pattern dimension was inferior to that in the second embodiment.

Examples 3 to 10 Exposures shown in Tables 1, 2 and 3 (in the case of X-rays, X-rays having a wavelength of 10 ° were used), and a resin and an acid generator were used. A photosensitive resin composition was prepared in the same manner, a pattern was formed by the same operation as in Example 2, and the same measurement was performed. The results are shown in Tables 1, 2 and 3.

As shown in Tables 1, 2 and 3, in each case, a good resolution pattern was obtained, and the pattern showed high dimensional uniformity.

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

[Table 3]

[0093]

The resist material used in the photosensitive resin composition of the present invention comprises a monomer containing at least one selected from the compound group (a) or the compound group (b). There is an effect that the used photosensitive resin composition can achieve high resolution and uniformity of pattern dimensions.

Further, in the method of using the photosensitive resin composition according to the present invention in the manufacture of a semiconductor device, the step of providing a film of the photosensitive resin composition on a semiconductor substrate includes the steps of: By performing the step of pattern-exposing the short-wavelength laser and the step of developing the exposed photosensitive resin composition film, the effect of obtaining a highly integrated semiconductor device capable of forming a fine pattern can be obtained. is there.

That is, according to claim 1 of the present invention, an alkali obtained by (co) polymerizing a monomer containing at least one kind selected from the compounds represented by the general formulas (I) to (IV). Since the material is a soluble resist material, the play of the pattern edge is improved, and the play of the pattern in the fine pattern is reduced.

According to a second aspect of the present invention, at least one of the compounds represented by the general formulas (I) to (IV) and 1 to 100 mol% are represented by the general formulas (I) to (IV). 0 to 99 mol% of a monomer having copolymerizability with the compound to be prepared
And (co) polymerization of (1) and (2), the backlash of the pattern in the fine pattern is further reduced.

According to claim 3 of the present invention, at least one of the compounds represented by the general formulas (I) to (IV) is represented by 20 to 80 mol% and represented by the general formulas (I) to (IV). 3. The alkali-soluble resist material according to claim 1, wherein the compound to be copolymerized with a copolymerizable monomer and 20 to 80 mol% of a copolymerizable compound further reduces pattern rattling in a fine pattern. .

According to claim 4 of the present invention, at least one selected from the group consisting of compounds in which the hydroxyl group and the carboxyl group of the compounds represented by the general formulas (I) to (IV) are substituted by acid labile groups. Monomer containing one (co)
Since it is a material for an alkali-insoluble resist obtained by polymerization, the play of the pattern edge is improved, and the play of the pattern in the fine pattern is reduced.

According to the fifth aspect of the present invention, at least one of the compounds represented by the general formulas (I) to (IV) in which the hydroxyl group and the carboxyl group are substituted with an acid labile group. 100 mol% and the general formulas (I) to (I)
5. The compound represented by the formula (V) wherein the hydroxyl group and the carboxyl group are substituted by an acid labile group and (co) polymerization of 0 to 99 mol% of a copolymerizable monomer.
Since it is the alkali-insoluble resist material described above, the rattling of the pattern in the fine pattern is further reduced.

According to the sixth aspect of the present invention, at least one of the compounds represented by the general formulas (I) to (IV) in which the hydroxyl group and the carboxyl group are substituted with an acid labile group is selected from the group consisting of 20 to 20. 80 mol% and the general formulas (I) to (I)
5. The alkali-insoluble compound according to claim 4, wherein the compound represented by V) is obtained by copolymerizing a compound having a hydroxyl group and a carboxyl group substituted by an acid labile group with 20 to 80 mol% of a copolymerizable monomer. Since the resist material is used, the rattling of the pattern in the fine pattern is further reduced.

According to claim 7 of the present invention, at least one of the compounds represented by the general formulas (I) to (IV) is represented by 10 to 90 mol% and represented by the general formulas (I) to (IV). Alkali-insoluble resist material obtained by copolymerizing 10 to 90 mol% of a monomer having an acid labile group which has a copolymerizability with a compound to be decomposed by an acid to generate a phenolic hydroxyl group or a carboxyl group. Therefore, rattling of the pattern in the fine pattern is further reduced.

According to an eighth aspect of the present invention, there is provided an alkali-soluble resist material according to the first, second or third aspect, an alkali-insoluble resist material and an acid generator according to the fourth, fifth, sixth or seventh aspect. And the alkali-soluble resist material / alkali-insoluble resist material is a photosensitive resin composition having a weight ratio of 0/100 to 90/10. The generated alkali-insoluble resist material becomes alkali-soluble, and a resist pattern with sharp edges with reduced pattern backlash can be obtained.

According to the ninth aspect of the present invention, the weight ratio of the resist material / acid generator is 90/10 to 99.
9. The photosensitive resin composition according to claim 8, wherein the ratio is 9 / 0.1, so that a resist pattern with sharp edges can be more easily obtained.

According to the tenth aspect of the present invention, when manufacturing a semiconductor device, a film is provided on a semiconductor substrate using a photosensitive resin composition, and light or radiation is applied to the photosensitive resin composition film. Is subjected to pattern exposure, and then the photosensitive resin composition film after the exposure is developed. This is a method of using the photosensitive resin composition according to claim 8 or 9 in the production of a semiconductor device. A reduced resist pattern with a clear edge can be easily obtained, and a semiconductor device with excellent performance can be manufactured.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 18/04 C08F 20/26 20/26 H01L 21/30 502R (72) Inventor Atsuko Fujino Chiyoda-ku, Tokyo 2-3-2 Marunouchi Mitsubishi Electric Corporation F-term (reference) 2H025 AB16 AC01 AC05 AC06 AD03 BE00 BG00 CB14 CB17 CB41 CB43 CB45 CB52 4J100 AB07P AE09P AE09Q AG08P AL08P AL08Q BA02Q BA03P BA15Q BA15Q BA15Q BA15Q BC53P CA04 DA38 FA02 JA38 JA46

Claims (10)

[Claims] 1. A compound of the general formula (I): (Wherein, R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms,
An alkoxyl group having 1 to 10 carbon atoms, a carboxyl group, a halogen atom, -SR ³ , an aromatic group having 6 to 20 carbon atoms, provided that R ³ is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, A
Is CH ₂ ＣC (R ² ) —COO— (CH ₂ ) _n —, CH ₂
ＣC (R ² ) —O—CO— (CH ₂ ) _n —, CH ₂ ＣＨCH—
_{O- (CH 2) n -,} CH 2 = C (R 2) -COO- (CH
_{2) n} -O-, provided that R ² is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, -CN, halogen atom, n represents a compound represented by the integer of 1 to 10) the general formula (II): Embedded image (Wherein R ¹ is the same as above, B is CH ₂ 2C (R ² )-
_{COO-, CH 2 = C (R} 2) -COO- (CH 2) n
_{-, CH 2 = C (R} 2) -O-CO- (CH 2) n-, C
H ₂ ＣＨCH—O—CH ₂ —, CH ₂ ＣＨCH—, m is 1 to 1
A compound represented by the formula (III): wherein R is an integer of 0, wherein R ² and n are as defined above. (Wherein R ¹ , R ² , and n are the same as those described above) and a compound represented by the general formula (IV): (Wherein R ¹ , R ² , and n are the same as described above). An alkali-soluble resist material obtained by (co) polymerizing a monomer containing at least one selected from the group consisting of compounds represented by the following formulas: 2. A compound having a copolymerizability with at least 1 to 100 mol% of the compounds represented by the general formulas (I) to (IV) and the compound represented by the general formulas (I) to (IV). 2. The material for an alkali-soluble resist according to claim 1, which is obtained by (co) polymerizing 0 to 99 mol% of a monomer. 3. A monomer having a copolymerizability with at least one of the compounds represented by the general formulas (I) to (IV) and 20 to 80 mol% of the compound represented by the general formulas (I) to (IV). 2. The copolymer of 20 to 80 mol% of a monomer.
The material for an alkali-soluble resist described in the above. 4. A compound containing at least one selected from the group consisting of compounds in which a hydroxyl group and a carboxyl group of the compounds represented by the general formulas (I) to (IV) are substituted with an acid labile group. An alkali-insoluble resist material obtained by co-polymerization. 5. A compound represented by the general formula (I) wherein at least one of the compounds represented by the general formulas (I) to (IV) in which a hydroxyl group and a carboxyl group are substituted by an acid labile group is 1 to 100 mol%. The compound represented by the formula (IV), wherein the hydroxyl group and the carboxyl group of the compound represented by the formula (IV) are substituted with an acid labile group, and 0 to 99 mol% of a copolymerizable monomer are (co) polymerized. Alkali-insoluble resist material. 6. The compound represented by the general formula (I), wherein at least one of the compounds represented by the general formulas (I) to (IV) in which the hydroxyl group and the carboxyl group are substituted by an acid labile group is 20 to 80 mol%. 5. The alkali according to claim 4, wherein the compound represented by the formula (IV) is obtained by copolymerizing a compound in which a hydroxyl group and a carboxyl group are substituted with an acid labile group and 20 to 80 mol% of a copolymerizable monomer. Insoluble resist material. 7. A compound having copolymerizability with at least one of the compounds represented by the general formulas (I) to (IV) in an amount of 10 to 90 mol% and the compounds represented by the general formulas (I) to (IV). ,
An alkali-insoluble resist material obtained by copolymerizing 10 to 90 mol% of a monomer having an acid labile group which is decomposed by an acid to produce a phenolic hydroxyl group or a carboxyl group. 8. An alkali-soluble resist material comprising the alkali-soluble resist material according to claim 1, 2 or 3, the alkali-insoluble resist material according to claim 4, 5, 6 or 7, and an acid generator. / A photosensitive resin composition in which the alkali-insoluble resist material has a weight ratio of 0/100 to 90/10. 9. The photosensitive resin composition according to claim 8, wherein the weight ratio of resist material / acid generator is 90/10 to 99.9 / 0.1. 10. When a semiconductor device is manufactured, a film is provided on a semiconductor substrate using a photosensitive resin composition, and the photosensitive resin composition film is subjected to pattern exposure to light or radiation. A method of using the photosensitive resin composition according to claim 8 or 9 for manufacturing a semiconductor device for developing a photosensitive resin composition film.