JPH0954432A - Photoresist composition - Google Patents

Abstract

(57) Abstract: To improve coating performance, solution stability and the like of a photoresist composition. SOLUTION: A fluorinated alkyl group-containing (meth) acrylate monomer (A), a silicone chain-containing ethylenically unsaturated monomer (B), and a polyoxyalkylene group-containing (meth) acrylate monomer. The present invention relates to a photoresist composition containing a copolymer with a monomer (C). [Effects] The photoresist composition according to the present invention can be applied uniformly without causing the coating film thickness of the photoresist composition and the occurrence of striation during spin coating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist composition sensitive to radiation such as ultraviolet rays, far ultraviolet rays, excimer laser light, and X-rays, and more specifically, semiconductor manufacturing processes such as LSI and IC, liquid crystal, The present invention relates to a photoresist composition for microfabrication, which is suitable for use in the production of substrates such as thermal heads, the production of PS plates, and other photofabrication processes and has excellent coating performance and solution stability.

[0002]

2. Description of the Related Art In the case of manufacturing a semiconductor device or liquid crystal by microfabrication using a resist agent, a resist agent is applied to the surface of a silicon wafer to form a photosensitive film, and ultraviolet rays, far ultraviolet rays, and excimer laser light are used. A pattern (image) is formed by a photolithography method of irradiating radiation such as X-rays to form a latent image, and then developing the latent image to form a negative or positive image.

By the way, in recent years, semiconductor elements have been used in ICs and LSs.
I and VLSI are highly integrated and high density,
Along with this, it is necessary to form a fine pattern of 1 μm or less. In photolithography of this semiconductor element, it is general to apply a photoresist agent to a silicon wafer by spin coating so that the thickness is about 1 to 2 μm. At this time, if the coating film thickness fluctuates or coating unevenness generally referred to as streaking occurs, the linearity and reproducibility of the pattern are deteriorated, and a resist pattern having desired accuracy can be obtained. There is a problem that there is no. At the present, resist patterns are becoming finer as semiconductor devices become more highly integrated, and it has become an important issue to suppress fluctuations in coating film thickness and generation of striations. In recent years, from the viewpoint of improving the productivity of semiconductor devices, etc., silicon wafers have been increasing in diameter from 6 inches to 8 inches or larger, but with this increase in diameter. In addition, suppression of the fluctuation of the coating film thickness and the occurrence of striation has become an extremely important issue.

Conventionally, as a measure for suppressing the fluctuation of the coating film thickness and the occurrence of streaking, there are disclosed in JP-A-63-98652, JP-A-2-247653 and JP-A-4-23.
No. 0549, Japanese Unexamined Patent Publication No. 4-340549, and Japanese Unexamined Patent Publication No. 5-113666, selection of resist solvent, and fluorine-based interface as described in Japanese Unexamined Patent Publication No. 7-21626. The addition of activators has been proposed.

[0005]

However, the effect of suppressing the fluctuation of the coating film thickness and the occurrence of streakage cannot be said to be sufficient by the selection of the above-mentioned solvent, and addition of the fluorine-based surfactant causes these problems. However, there is a problem that when the silicon wafer has a large diameter, the conventional fluorine-based surfactant cannot sufficiently improve the coating property.

Further, in the case of the conventional fluorine-containing surfactant, there is a problem that the effect of suppressing the fluctuation of the coating film thickness and the occurrence of the above-mentioned streak is insufficient. Of interacting with a resin and a photosensitizer to form fine particles (also referred to as submerged particles) that cannot be observed with the naked eye, and impede fine resist pattern formation. Therefore, there is a problem in that bubbles are trapped in the resist agent to hinder the formation of a fine resist pattern.Furthermore, due to the water repellency of the fluorochemical surfactant, the wettability of the developing solution is poor and uneven development is caused. There was a problem that it would occur.

The above problems have also been observed when applying a liquid crystal resist agent to a liquid crystal substrate.

[0008]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to solve the above problems, the copolymerization component was found to contain a fluorinated alkyl group-containing (meth) acrylate monomer and a silicone chain. By adding a fluorine-containing polymer, which is a contained ethylenically unsaturated monomer, to a photoresist agent, even if the silicon wafer for semiconductor device production has a large diameter or the liquid crystal substrate has a large diameter. In addition, it is possible to achieve uniform coating without touching the coating thickness of the photoresist agent and generation of streaking during spin coating. In addition, the generation of particles in the liquid, which has been a problem in the past, There is no problem of the inclusion of bubbles in the liquid, and the problem of uneven development is eliminated due to the impediment of the wettability of the developing solution, and the formation of the fine resist pattern and the high liquid crystal pattern, which are indispensable for high integration of semiconductor elements, are eliminated. Fine Onsets saw that becomes possible, which resulted in the completion of the present invention.

That is, the present invention comprises a copolymer of a fluorinated alkyl group-containing (meth) acrylate monomer (A) and a silicone chain-containing ethylenically unsaturated monomer (B). And preferably contains a polyoxyalkylene group-containing (meth) acrylate monomer as a copolymerization component, and more preferably a polyoxyalkylene group-containing (meth) acrylate monomer and the number of carbon atoms. Provided is a photoresist composition containing a (meth) acrylate monomer having 6 or more alkyl groups in its side chain.

In the present invention, (meth) acrylate is a generic term for methacrylic acid, acrylate, fluoroacrylate and chlorinated acrylate. In the present invention, as the fluorinated alkyl group-containing (meth) acrylate monomer (A), it is possible to use any known and commonly used one, and specifically, the following general formula (a) can be used. The compound represented by

That is,

[0012]

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[Wherein R _f is a C 1-20 perfluoroalkyl group or a partially fluorinated alkyl group,
It may be linear, branched, or one in which an oxygen atom is interposed in the main chain, such as-(OCFCF ₂ ) ₂ CF (CF ₃ ) ₂ , wherein R ₁ is H, CH ₃ , Cl, or F. , X is a divalent linking group, specifically-(CH ₂ ) _n- ,

[0014]

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[0015]

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[0016]

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(However, n is an integer of 1 to 10, and R ₂
Is H or an alkyl group having 1 to 6 carbon atoms. ),

[0018]

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[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

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[0022]

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Or

[0024]

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Etc. and a is 0 or 1. And a compound represented by the general formula

[0026]

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Compounds having a plurality of perfluoroalkyl groups in the molecule as described above [wherein l is an integer of 1 to 14]. ].
Specific examples of the fluorinated alkyl group-containing (meth) acrylate include the following.

[0028]

[Chemical 12]

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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Needless to say, the present invention is not limited to the above specific examples. The fluorinated alkyl group-containing (meth) acrylate monomer (A) may be a mixture of two or more kinds of compounds having different structures.

In the present invention, the fluorinated alkyl group-containing (meth) acrylate monomer (A) is used for suppressing the contact of the coating film thickness of the photoresist composition with the coating property and preventing the occurrence of streaks. It is an essential monomer component for exerting the performance, and if it is omitted, the above performance becomes poor.

From the viewpoint of improving the coating property of the photoresist composition according to the present invention and the performance of preventing the occurrence of striation, the perfluoro in the (meth) acrylate monomer (A) containing a fluorinated alkyl group is used. The carbon number of the alkyl group or partially fluorinated alkyl group is preferably 3 or more, and particularly preferably 6 or more.

The silicone chain-containing ethylenically unsaturated monomer (B) according to the present invention means an α, β-unsaturated group through a divalent linking group at one end or both ends of the polysiloxane chain. That is, a vinyl group, an acryloyl group, or a methacryloyl group is linked, and specific examples thereof include the general formula (c-1)

[0038]

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[In the formula, R ₃ and R ₄ are alkyl groups having 1 to 20 carbon atoms or phenyl groups, which may be the same or different, and may be the same or different for each siloxy unit, and p is 3 Is an integer of ˜520, q is 0 or 1, X ₂ is a divalent linking group, —CH ₂ CH (OH) CH ₂ OCO—, — (CH ₂ ).
_n1 NHCH ₂ CH (OH) CH ₂ OCO-,-(CH ₂ ) _n1 OCO-,-(CH ₂ ) _n1 -O- (CH
_{2) m1} OCO-, or _{-OCH 2 CH (OH) CH 2} OCO- [ where, n ₁ m ₁ is 2
Is an integer from 6 to 6. R ₁ is the same as described above, and Z ₁ is a methyl group, a phenyl group, or CH ₂ = C (R ₁ )-(X ₂ ) _q
-Yes. ] The compound represented by these, or general formula (c-
2)

[0040]

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[Wherein R ₅ , R ₅ ′, R ₅ ″, R ₆ ,
R ₆ ′, R ₆ ″, R ₇ , R ₇ ′, R ₇ ″ are an alkyl group or a phenyl group having 1 to 20 carbon atoms, which may be the same or different, and r, s, t are 0 or An integer of 1 to 200, which may be the same or different, and X ₂ , q,
R ₁ is as defined above. ] The compound represented by this is mentioned.

The following are more specific examples of the monomer containing a silicone chain.

[0043]

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[0044]

[Chemical 21]

[0045]

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[0046]

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However, Me and Ph represent a methyl group and a phenyl group, respectively. As the ethylenically unsaturated group of the silicone chain-containing ethylenically unsaturated monomer (B), any of a vinyl group, an acryloyl group and a methacryloyl group is possible, but an acryloyl group or a methacryloyl group is preferred in view of polymerization reactivity. Since the group is excellent, those containing these are particularly preferable.

The silicone chain-containing ethylenically unsaturated monomer (B) may be a mixture of two or more kinds of compounds having different structures. In the present invention, the silicone chain-containing ethylenically unsaturated monomer (B) is used for improving the coating property of the photoresist agent and preventing the occurrence of streaks, preventing the generation of particles in the liquid, and the photoresist agent. It is an essential monomer component from the viewpoint of preventing inclusion of bubbles in the inside, and if it is lacking, the above performance becomes poor.

Application of the photoresist composition of the present invention and prevention of striation, prevention of particles in solution, prevention of inclusion of bubbles in photoresist composition, and wettability of developer. From the viewpoint of preventing uneven development due to defects, the molecular weight of the silicone chain portion of the silicone chain-containing ethylenically unsaturated monomer (B) is 5,000.
It is preferably 0 or less, particularly preferably 1,000 or less, and the structure of the silicone chain portion is preferably a branched type structure as shown in the general formula (c-2). In (c-2), those in which r, s, and t are 0 are particularly preferable.

In the copolymer according to the present invention, it is extremely important to simultaneously contain a fluorinated alkyl group and a silicone chain in the molecule at the same time. Excellent coating properties that conventional photoresist agents cannot achieve, prevention of streakage, prevention of particles in solution, reduction of bubble entrapment, and improvement of wettability of developer during development. Accordingly, excellent developability is exhibited.

Therefore, in the copolymer of the present invention, the (meth) acrylate monomer (A) containing a fluorinated alkyl group is used.
Alternatively, when either one of the silicone chain-containing ethylenically unsaturated monomer (B) is lacking, excellent coatability as described in the present invention, prevention of streak generation, prevention of generation of particles in liquid, The excellent developability due to the reduction of the inclusion of bubbles and the improvement of the wettability of the developing solution at the time of development are not exhibited.

The copolymer according to the present invention is added to a photoresist composition to further improve various performances of the photoresist composition and to improve compatibility stability with the photoresist agent. As the constituent monomer, in addition to the above-mentioned monomer (A) and monomer (B), it is possible to use a non-fluorine- and non-silicone-based ethylenically unsaturated monomer (C).

Specific examples of the non-fluorine and non-silicone type ethylenically unsaturated monomer (C) include the followings. That is, styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylpyrrolidone, vinylsulfonic acid, vinyl acetate, and other fatty acid vinyls, and α, β-ethylenically unsaturated carboxylic acids, that is, acrylic acid. As a derivative of a monovalent or divalent carboxylic acid such as methacrylic acid, maleic acid, fumaric acid or itaconic acid, or a derivative of an α, β-ethylenically unsaturated carboxylic acid, an alkyl group having 1 to 18 carbon atoms (meta )
Acrylic acid alkyl ester (hereinafter, this expression generically refers to both acrylic acid alkyl ester and methacrylic acid alkyl ester), that is, (meth) acrylic acid methyl, ethyl, propyl, butyl, octyl, 2
-Ethylhexyl, decyl, dodecyl, stearyl ester and the like, and hydroxyalkyl ester of (meth) acrylic acid having 1 to 18 carbon atoms, that is, 2-hydroxyethyl ester, hydroxypropyl ester, hydroxybutyl ester and the like can be mentioned.

The (meth) acrylic acid has 1 to 18 carbon atoms.
Aminoalkyl ester of dimethylaminoethyl ester, diethylaminoethyl ester, diethylaminopropyl ester, etc., and (meth) acrylic acid, an ether oxygen-containing alkyl ester having 3 to 18 carbon atoms,
For example, methoxyethyl ester, ethoxyethyl ester, methoxypropyl ester, methylcarbyl ester, ethylcarbyl ester, butylcarbyl ester, etc. Further, examples of the monomer containing a bridge bond include dicyclopentanyloxylethyl (meth) acrylate, isobornyl. Oxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth)
Acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, etc., and a degree of polymerization of 1
.About.100 polyethylene glycol, polypropylene glycol, and polyalkylylene glycol mono (meth) acrylic acid ester or di (meth) acrylic acid ester such as a copolymer of ethylene oxide and propylene oxide, Alternatively, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and copolymers of ethylene oxide and propylene oxide, which have a degree of polymerization of 1 to 100 and are capped with an alkyl group having 1 to 6 carbon atoms, can be used. Mono (meth) acrylic acid ester, alkyl vinyl ether having 1 to 18 alkyl carbon atoms, such as methyl vinyl ether, propyl vinyl ether, dodecyl vinyl ether, etc., glycidyl ester of (meth) acrylic acid, that is, glycidyl methacrylate, glycy Le acrylate, also Sartomer styrene macromonomer 4500, Shin-Nakamura Chemical Co., macromonomers such as NK ester M-230G and the like.

Further, γ-methacryloxypropylmethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropylmethyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, vinyl. Silane-capping group-containing monomers such as trimethyloxysilane, and acrylic acid as a monomer containing a polar group, especially an anionic group or a hydroxyl group in the molecule,
Methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2-acrylamido-2-methylpropanesulfonic acid, partially sulfonated styrene, mono (acryloyloxyethyl) acid phosphate, mono (methacryloxyethyl) acid Examples thereof include phosphate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like.

Needless to say, the present invention is not limited to the above specific examples. According to the knowledge of the present inventors, excellent coating properties of the photoresist composition according to the present invention, prevention of generation of streakage, prevention of generation of particles in liquid, reduction of inclusion of bubbles, and development From the viewpoint of further improving various properties such as excellent developability associated with the improvement in the wettability of the developing solution, the non-fluorine- and non-silicone-based ethylenically unsaturated monomer (C) has polyethylene in the side chain. Mono (meth) acrylic acid ester or di (meth) acrylic acid ester of polyalkylene glycol such as glycol, polypropylene glycol, and a copolymer of ethylene oxide and propylene oxide, or having 1 to 10 carbon atoms Polyethylene glycol, polypropylene glycol, and ethylene oxide and propylene having a degree of polymerization of 1 to 100 capped by an alkyl group of 6 It is preferable to use a mono (meth) acrylic acid ester of polyalkylene glycol such as a copolymer with an oxide and / or a (meth) acrylic acid ester having a side chain of an alkyl group having 4 or more carbon atoms. . Further, as a side chain, a polyethylene glycol, a polypropylene glycol, and a polyalkylene glycol mono (meth) acrylic acid ester or di (meth) acrylic acid ester such as a copolymer of ethylene oxide and propylene oxide is used. (Meth) acrylic acid ester of ethylene, propylene oxide and polyethylene glycol
It is more preferable to use di (meth) acrylic acid ester of the same, and it is more preferable to use both of them at the same time.

The method for producing the copolymer according to the present invention is not limited at all, and based on the known mechanism, such as radical polymerization method, cationic polymerization method and anionic polymerization method, solution polymerization method and bulk polymerization method. Although it can be produced by an emulsion polymerization method or the like, the radical polymerization method is particularly convenient and industrially preferable.

In this case, as the polymerization initiator, those known in the art can be used, for example, peroxides such as benzoyl peroxide and diacyl peroxide, azobisisobutyronitrile, phenylazotriphenylmethane and the like. Azo compounds, metal chelate compounds such as Mn (acac) 3, and the like.

Further, if necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, octyl thioglycolic acid, or a coupling agent such as γ-mercaptopropyltrimethoxysilane. An additive such as a chain transfer agent can be used for the group-containing thiol compound.

The fluorine-based random or block copolymer according to the present invention can also be obtained by photopolymerization in the presence of a photosensitizer or a photoinitiator or polymerization using radiation or heat as an energy source.

The polymerization can be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent from the viewpoint of workability. Solvents include ethanol, isopropyl alcohol, n-butanol, iso-butanol.
Alcohol, alcohols such as tert-butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate and butyl acetate, polar solvents such as dimethylformamide and dimethyl sulfoxide, 1 Halogen-based solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene and xylene, and fluorine such as perfluorooctane and perfluorotri-n-butylamine. Any of the modified inner liquids can be used.

In the copolymer according to the present invention, the copolymerization ratio of the fluorinated alkyl group-containing (meth) acrylate monomer (A) and the silicone chain-containing ethylenically unsaturated monomer (B). Is 100: 1 to 1: 100 by weight,
Excellent coating properties in the photoresist composition according to the present invention, prevention of occurrence of streakage, prevention of generation of particles in a liquid, reduction of inclusion of bubbles, excellent with improvement in wettability of a developer during development In order to effectively exert the effects such as developing property and cleaning property, 40: 1 to 1:40 are preferable. In the fluorine-based copolymer according to the present invention, when a non-fluorine- and non-silicone-based ethylenically unsaturated monomer (C) is introduced as a copolymerization component, (C) to (A) + (B) The weight ratio of 1) is 100: 0 to 1: 1,000, and 100: 0 to 1: 100 is particularly preferable.

The molecular weight of the copolymer according to the present invention is
Mn = 1,000 to 2,000,000, excellent coating properties according to the present invention, prevention of streakage, prevention of particles in solution, reduction of inclusion of bubbles, and developer for development From the viewpoint of exhibiting excellent developability associated with the improvement of the wettability, 1,000 to 500,000 is preferable, and 1,000 to 100,000 is particularly preferable.

The photoresist composition according to the present invention comprises the above copolymer and a known and commonly used photoresist agent.
As the photoresist agent that can be combined with the fluorine-based copolymer according to the present invention, any known and commonly used photoresist agent can be used without any limitation.

Usually, the photoresist agent comprises (1) an alkali-soluble resin, (2) a radiation-sensitive substance (photosensitive substance), (3) a solvent, and (4) other additives as required.

As the (1) alkali-soluble resin used in the present invention, any resin can be used without any limitation as long as it is a resin which is soluble in the alkaline solution constituting the developing solution used when the resist is patterned. It is possible, for example, phenol, cresol, xylenol, resorcinol,
Fluoroglycinol, aromatic hydroxy compounds such as hydroquinone and at least one of these alkyl-substituted or halogen-substituted aromatic compounds and formaldehyde, acetaldehyde, a novolak resin obtained by condensation with an aldehyde compound such as benzaldehyde,
Vinylphenol compounds such as o-vinylphenol, m-vinylphenol, p-vinylphenol and α-methylvinylphenol, and polymers or copolymers of these halogen-substituted compounds, acrylic acid, methacrylic acid , An acrylic acid-based or methacrylic acid-based polymer or copolymer such as hydroxyethyl (meth) acrylate, polyvinyl alcohol, a quinonediazide group, a naphthoquinoneazide group through a part of the hydroxyl groups of the various resins, A modified resin having a radiation-sensitive group such as an aromatic azide group or an aromatic cinnamoyl group introduced therein can be mentioned, and these resins can be used in combination.

Other alkali-soluble resins include JP-A-58-105143 and JP-A-58-20343.
4, JP-A-59-231534, JP-A-59-231534
JP-A No. 24545, JP-A-60-121445, JP-A-61-226745, JP-A-61-2
No. 60239, JP-A-62-36657, JP-A-62-123444, JP-A-62-1785.
No. 62, JP-A-62-284354, JP-A-63-24244, JP-A-63-113451, JP-A-63-220139, JP-A-63-214139
98652, JP-A-2-125260, JP-A-3-144648, JP-A-2-247563
JP, JP-A-4-291258, JP-A-4-3258
40549, JP-A-4-368864, JP-A-5-113666, JP-A-6-186735
Publication, USP 3,666,473, USP
4,115,128, USP 4,173,47
No. 0 specification, USP 4,526,856 specification, and the like,
Further, it is also possible to use the publicly known ones described in the publication, Teruhiko Yonezawa, "Introduction to PS Version," Printing Society Press (1993).

Further, as the alkali-soluble resin, it is possible to use a urethane resin containing an acidic group such as carboxylic acid or sulfonic acid in the molecule, and to use these urethane resins in combination with the above alkali-soluble resin. Is also possible. As the alkali-soluble resin, two or more different types may be mixed and used.

As the radiation-sensitive substance (photosensitive substance) (2) according to the present invention, any known and commonly used substances can be used without any limitation. Deep ultraviolet, excimer laser light,
Irradiation with X-rays, electron beams, ion beams, molecular beams, γ-rays, etc. can be used without any limitation as long as it is a substance that changes the solubility of the alkali-soluble resin in the developing solution.

Preferred radiation-sensitive substances are quinonediazide compounds, diazo compounds, diazide compounds, onium salt compounds, halogenated organic compounds, halogenated organic compounds / organometallic compound mixtures, organic acid ester compounds, organic acid amides. Examples thereof include compounds, organic acid imide compounds, and poly (olefin sulfone) compounds described in JP-A-59-152.

Specific examples of the quinonediazide compound include, for example, 1,2-benzoquinoneazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, and 1,2-naphthoquinonediazide-5.
Sulfonate, 2,1-naphthoquinonediazide-
4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, 1,2-benzoquinone azide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2
-Naphthoquinonediazide-5-sulfonic acid chloride,
Examples thereof include sulfonic acid chlorides of quinonediazide derivatives such as 2,1-naphthoquinonediazide-4-sulfonic acid chloride and 2,1-naphthoquinonediazide-5-sulfonic acid chloride.

As the diazo compound, a salt of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, for example, hexafluorophosphate, tetrafluoroborate, perchlorate or periodate and the above condensate. Inorganic salt of diazo resin that reacts with
As described in P3,300,309,
An organic salt of a diazo resin, which is a reaction product of the condensate and a sulfonic acid, is exemplified.

Specific examples of the azide compound and the diazide compound include azidochalcone acids, diazidobenzalmethylcyclohexanones and azidocinnamylideneacetophenones as described in JP-A-58-203438, Nippon Kagaku. Journal No. 12, p1708-1
714 (1983), aromatic azide compounds and aromatic diazide compounds.

The halogenated organic compound is not particularly limited as long as it is a halide of an organic compound, and various known compounds can be used. Specific examples thereof include a halogen-containing oxadiazol compound and a halogen-containing triazine. Compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds,
Halogen-containing thiazole-based compounds, halogen-containing oxazole-based compounds, halogen-containing trizol-based compounds, halogen-containing 2-pyrone-based compounds, halogen-containing aliphatic hydrocarbon-based compounds, halogen-containing aromatic hydrocarbon-based compounds, Various compounds such as other halogen-containing heterocyclic compounds and sulfenyl halide compounds, for example, tris (2,3-dibromopropyl) phosphate and tris (2,3-dibromo-3-chloropropyl) phosphate
Chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenylallyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis (bromoethyl ether) -Tel)
Tetrabromobisphenol A, bis (chloroethyl ether) tetrachlorobisphenol A, tris (2,
3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyethoxy-3,5
Also included are compounds used as halogen-based flame retardants such as -dibromophenyl) propane, and compounds used as organic chloro pesticides such as dichlorophenyltrichloroethane.

Specific examples of the organic acid ester include carboxylic acid ester and sulfonic acid ester. Specific examples of the organic acid amide include carboxylic acid amide and sulfonic acid amide. Further, specific examples of the organic acid imide include carboxylic imide, sulfonic imide and the like.

In addition, as radiation-sensitive substances according to the present invention, JP-A-58-105143 and JP-A-58-2 are used.
03434, JP-A-59-231534,
JP-A-60-24545, JP-A-60-1214
No. 45, JP-A-61-226745, JP-A-61-260239, JP-A-62-36657, JP-A-62-123444, and JP-A-62-263.
178562, JP-A-62-284354, JP-A-63-24244, JP-A-63-11
No. 3451, JP-A-63-220139, JP-A-63-98652, JP-A-2-125260
JP, JP-A-3-144648, JP-A-2-2-2
47653, JP-A-4-291258, JP-A-4-340549, JP-A-4-368864
JP-A-5-113666, JP-A-5-13666
86735, USP 3,666,473, USP 4,115,128, USP 4,1
73,470 specification, USP 4,526,856 specification, etc. can be used. Further, two or more different types of radiation-sensitive substances may be used.

In the photoresist composition, the proportion of the radiation-sensitive substance is 1 to 100 parts by weight, preferably 3 to 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin.
0 parts by weight.

In the present invention, for the purpose of adjusting the solubility of the alkali-soluble resin in a developing solution, an acid-crosslinking compound can be used if necessary. In the present invention, the acid-crosslinkable compound is crosslinked during irradiation in the presence of a compound capable of generating an acid under irradiation of the above-mentioned radiation, and reduces the solubility of the alkali-soluble resin in the irradiated portion of the radiation in an alkali developing solution. Any known and commonly used substance can be used without any limitation. Among them, C-
A compound having an OR group (wherein R is a hydrogen atom or an alkyl group) in the molecule, or a compound having an epoxy group is preferable.

Specific examples of the compound having a C—O—R group include, for example, JP-A-2-247653 and JP-A-5-26553.
Melamine-formaldehyde resin, alkyl ether melamine resin, benzoguanamine resin, alkyl ether benzoguanamine resin, urea resin, alkyl ether urea resin described in
Examples thereof include urethane-formaldehyde resins and phenolic compounds containing an alkyl ether group. As the acid crosslinkable compound, two or more different types may be mixed and used. Further, in the photoresist composition, the compounding ratio of the acid-crosslinking compound is 0.1 to 100 parts by weight, and 1 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. If the blending ratio of the acid crosslinkable compound is too small,
It becomes difficult to form the resist pattern, and on the contrary, if the resist pattern is excessively large, a development residue may occur.

As the solvent (3), it is possible to use a conventionally known solvent without any limitation. Conventionally, when a photoresist agent is applied to a silicon wafer, in order to improve coatability, prevent occurrence of streakage, and improve developability, JP-A-62-36657 and JP-A-4-340 are used.
Various solvent compositions have been proposed, as described in Japanese Patent Application Publication No. 549, Japanese Patent Application Laid-Open No. 5-113666, and the like.
If the copolymer according to the present invention is used, excellent coating properties, prevention of streak generation, prevention of particles in liquid, and inclusion of bubbles are achieved without such troublesome solvent adjustment. It is possible to obtain excellent developability due to the reduction of the amount and the improvement of the wettability of the developing solution at the time of development. Further, in recent years, from the viewpoint of safety to the human body, from a solvent such as ethyl cellosolve acetate which has been conventionally used for a photoresist agent,
Highly safe solvents such as ethyl lactate have come to be used, and careful attention is required to prevent coating properties and the occurrence of streaks.However, use of the fluorocopolymer according to the present invention If so, there is an advantage that such problems can be eliminated. Therefore, in the photoresist composition according to the present invention, it is possible to select a wider range of solvents than ever before.

Examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, butyrolactone, methanol, ethanol, n-propyl alcohol. , Iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentano
Alcohols such as alcohol, heptanol, octanole, nonanol, decanol, etc., ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethers such as dioxane, ethylene glycol monomethyl ether. -Alcohol ethers such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Such as ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, etc. Esters, - propionic acid methyl,
Such as ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate and butyl 2-methoxypropionate. Monocarboxylic acid esters, cellosolve acetate, methyl cellosolve acetate
, Ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, and other cellosolve esters, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether. Propylene glycols such as teracetate and propylene glycol monobutyl ether acetate, diethylelglycol monomethyl ether, diethylelglycol monoethyl ether, diethylelglycol dimethyl ether, diethylylglycol diethylether, diethylylglycol methylethyl ether and the like. Diethylene glycol, trichloroethylene, freon solvent, halogenated hydrocarbons such as HCFC, HFC, perfluoroocta Perfluorinated solvents, such as toluene, aromatic ethers such as xylene, dimethyl acetylene, dimethylformamide, N- methylacetamide,
A polar solvent such as N-methylpyrrolidone, "Solvent Pocket Handbook" (edited by the Society of Synthetic Organic Chemistry, Ohmsha)
And the solvents described in JP-A-58-105143, JP-A-58-203434, and JP-A-59-
231534, JP-A-60-24545,
JP-A-60-121445 and JP-A-61-226
745, JP-A 61-260239, JP-A 62-36657, and JP-A 62-123444.
JP-A-62-178562, JP-A-62-78562
-284354, JP-A-63-24244, JP-A-63-113451, and JP-A-63-2.
2013, JP-A-63-98652, JP-A-2-125260, JP-A-3-144648.
Japanese Patent Laid-Open No. 2-247653, Japanese Laid-Open Patent Publication No. 4-2
91258, JP-A-4-340549, JP-A-4-368864, JP-A-5-113666.
Japanese Patent Laid-Open No. 6-186735, USP 3,6
66,473, USP 4,115,128, USP 4,173,470, USP 4,
It is possible to use the publicly known and used solvents described in the specification of 526,856 and the like. As the solvent of the photoresist agent according to the present invention, two or more different solvents can be mixed and used.

In the photoresist composition according to the present invention, the blending ratio of the solvent can be appropriately adjusted depending on the required film thickness when applying the photoresist composition to the substrate and the application conditions, but in general, 10 to 1 per 100 parts by weight of the total of alkali-soluble resin and radiation-sensitive substance
50,000 parts by weight, preferably 50 to 2,000
Parts by weight.

In the present invention, the blending ratio of the copolymer according to the present invention can be appropriately adjusted according to the required film thickness and coating conditions when the photoresist composition is coated on the substrate, and the type of solvent used. However, usually alkali-soluble resin 1
The amount is 0.0001 to 5 parts by weight, preferably 0.0005 to 1 part by weight, relative to 00 parts by weight. In the photoresist composition according to the present invention, the presence of the fluorine-based copolymer is extremely important, and when the fluorine-based copolymer is lacking, excellent coatability according to the present invention, prevention of streak generation, in liquid This will be a hindrance in preventing the generation of particles, reducing the inclusion of bubbles, and exhibiting excellent developability associated with improvement in the wettability of the developing solution during development.

In the photoresist composition of the present invention, if necessary, a known and conventional surfactant, storage stabilizer,
It is possible to add adhesion enhancers such as pigments, dyes, fluorescent agents, color formers, plasticizers, thickeners, thixotropic agents, resin dissolution inhibitors, silane coupling agents and the like.

The coating method of the photoresist composition according to the present invention includes spin coating, roll coating, dip coating, spray coating, prede coating, curtain coating and the like. It is possible to widely use known and commonly used coating methods.

[0086]

BEST MODE FOR CARRYING OUT THE INVENTION A preferred embodiment of the present invention will be described. First, 1 to 40 parts by weight of a silicone chain-containing ethylenically unsaturated monomer based on 40 to 1 part by weight of a fluorinated alkyl group-containing unsaturated monomer, and further a fluorinated alkyl group-containing ethylenically unsaturated monomer And a silicone chain-containing ethylenically unsaturated monomer in a total amount of 100 to 1 part by weight, and blending 0 to 10 parts by weight of a non-fluorine- and non-silicone type ethylenically unsaturated monomer, a polymerization initiator and a chain. The copolymer according to the present invention is produced by radical polymerization in the presence of a transfer agent or the like.

Among the above monomers, the fluorinated alkyl group-containing unsaturated monomer is a perfluoroalkyl group-containing (meth) acrylate having 6 or more carbon atoms, and the silicone chain-containing unsaturated monomer is , A vinyl group, an acryloyl group, a methacryloyl group or the like through a divalent linking group at one or both ends of a silicone chain having a molecular weight of 5000 or less,
A non-fluorine-containing, silicone-based ethylenically unsaturated monomer using a compound in which a β-unsaturated group is linked is used, and its side chain is a mono (meth) acrylic acid ester of polyalkylene glycol such as polyethylene glycol and / or carbon. A (meth) acrylic acid ester having an alkyl group of 4 or more in the side chain is used.

Phenolic resin 10 which is a condensate of phenol and formaldehyde as an alkali-soluble resin
0 parts by weight, 2,3,4-trihydroxybezophenone and o-naphthoxydiazide-5 as a radiation sensitive substance
3 to 50 parts by weight of sulfonyl chloride, 50 to 2000 parts by weight of the solvent per 100 parts by weight of the total of the alkali-soluble resin and the radiation-sensitive substance, and 0.0005 to 1 part by weight per 100 parts by weight of the alkali-soluble resin. A photoresist composition of the present invention is prepared by mixing some of the above copolymers.

The photoresist composition according to the present invention comprises L
It can be suitably used in a semiconductor manufacturing process such as SI and IC, a substrate such as a liquid crystal and a thermal head, a PS plate, and other photofabrication processes.

[0090]

EXAMPLES The present invention will be described in more detail below with reference to specific synthesis examples and examples according to the present invention, but it goes without saying that the invention is not limited to these specific examples. Example 1 18 parts by weight of a fluorinated alkyl group-containing (meth) acrylate monomer a-1 was placed in a glass flask equipped with a stirrer, a condenser and a thermometer, and a silicone chain-containing ethylenically unsaturated monomer c was added. 2-1 (r = s = t = 0) 12 parts by weight, 53 parts by weight of a monomethacrylate compound having a side chain of a copolymer of ethylene oxide and propylene oxide having a molecular weight of 400 53 parts by weight, both ends of tetraethylene glycol Was charged with 4 parts by weight of a methacrylic acid compound, 8 parts by weight of methyl methacrylate, and 350 parts by weight of isopropyl alcohol (hereinafter abbreviated as IPA), and the mixture was refluxed in a nitrogen gas stream. Below, 1 part by weight of azobisisobutyronitrile (hereinafter abbreviated as AIBN) as a polymerization initiator and 5 parts by weight of lauryl mercaptan as a serial transfer agent were added, and the mixture was refluxed for 7 hours to complete the polymerization.

The polystyrene reduced molecular weight of this polymer as determined by gel permeation graph (hereinafter abbreviated as GPC) was Mn = 5,000. This copolymer is referred to as a fluoropolymer 1.

Synthesis Examples 2 to 19 Various fluorinated alkyl group-containing (meth) acrylate monomers (A), silicone chain-containing ethylenically unsaturated monomers (B), non-fluorine and non-silicone A fluorine compound was obtained in the same manner as in Synthesis Example 1 except that the systemic ethylenically unsaturated monomer (C) and the chain transfer agent were used in the proportions shown in Tables 1 to 3. The results of measuring the molecular weight of these polymers are shown in Tables 1 to 3. In addition, the charging ratio of each raw material in Tables 1 to 3 is parts by weight, and the symbols of the raw materials indicate the compounds described in the text.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

[Table 3]

Examples 1 to 18 and Comparative Examples 1 to 9 Condensate 2 of 2,3,4-trihydroxybezophenone and o-naphthoxydiazide-5-sulfonyl chloride
7 parts by weight of 100 parts by weight of a novolak resin obtained by condensing cresol and formaldehyde are mixed with 400 parts of ethyl lactate.
A solution was prepared by dissolving it in parts by weight, and Synthesis Examples 1 to 19 were prepared.
The fluorine-containing copolymer or commercially available fluorine-containing surfactant is added to the solid content in the solution so as to have a predetermined concentration, and is microfiltered with a 0.1 μm PTFE filter to form a photoresist composition. The thing was prepared. This photoresist composition was spin-coated on a silicon wafer having a diameter of 8 inches at a rotation speed of 4,200 rpm and then 90 ° C.
By heating and drying for 30 minutes, a wafer having a resist film with a film thickness of 1.5 μm was obtained. The following items were evaluated for the silicon wafer having the resist film obtained as described above.

The photoresist solution was also evaluated as follows. The evaluation results are shown in Tables 4 and 5.

[0098]

[Table 4]

[0099]

[Table 5]

In the table, the added amount (ppm) of the fluoropolymer or the commercially available surfactant is the solid content relative to the solid content of the photoresist agent. The solvent of the photoresist composition shown in the above examples was examined in place of propylene glycol monomethyl ether or methyl ethyl ketone / 2-heptanone (1/1 weight ratio), and it was the fluoropolymer according to the present invention. No. 1 to No. For 15,
Good results were obtained in all tests, while No.
16-No. Good results were not obtained with 19 fluoropolymers and the conventional commercially available fluorosurfactants.

<Test Method and Evaluation Criteria> (1) Foaming Property 50 cc of the photoresist solution prepared as described above.
Was evaluated in a 100 cc sample bottle with a sealed stopper, and 30 c
It permeated 50 times at a rate of 2 times per second with an amplitude of m, and the state of bubbles after standing was confirmed.

B: Bubbles disappear with standing. Δ: One minute after the start of standing, bubbles disappeared. ×: Air bubbles are present even one minute after the start of standing. (2) Striation The resist film surface was magnified 100 times with an optical microscope, and the occurrence of streak was observed.

A: No occurrence of streak is observed. Δ: Striation is slightly recognized. X: Striation is remarkably recognized. (3) Surface Roughness The surface roughness of the resist film was measured using a surface roughness meter "Taristep" manufactured by Rankteller Hobson. The number of measurements was 21 points / 1 wafer, and the average value of 21 measurement points was determined. (4) Paintability The surface of the resist film was visually observed, and the presence or absence of unpainted residue was observed.

◯: There is no unpainted portion. Δ: A residue was found on a very small part of the periphery of the wafer. ×: A part of the periphery of the wafer was left uncoated.

Examples 19 to 36, Comparative Examples 10 to 18 Polyvinylphenol (weight average molecular weight 5,000) 1
Alkyl etherified melamine-formaldehyde resin (manufactured by Sanwa Chemical Co., Ltd.,
Nikarac MW-30) 20 parts by weight, Bisphenol S
2 parts by weight of 2,3-dibromopropyl ether was dissolved in 400 parts by weight of ethyl 2-methoxypropionate, and further, the fluoropolymer (I) of Synthesis Examples 1 to 19 or a commercially available fluorosurfactant was added thereto. The agent was added so as to have a predetermined concentration with respect to the solid content in the solution, and microfiltered with a 0.1 μm PTFE filter to prepare a photoresist composition. This photoresist composition was spin-coated on a silicon wafer having a diameter of 8 inches at a rotation speed of 4,200 rpm and then dried by heating at 100 ° C. for 90 seconds to obtain a wafer having a resist film having a thickness of 1.0 μm. Got
Examples 1 to 18 of the silicon wafer having the resist film and the photoresist solution obtained as described above
The same test was performed.

The evaluation results are shown in Tables 6 and 7.

[0107]

[Table 6]

[0108]

[Table 7]

In the table, the added amount (ppm) of the fluoropolymer or the commercially available surfactant is the solid content relative to the photoresist solid content. The solvent of the photoresist agent shown in the above example was replaced with propylene glycol monomethyl ether.
Tell or methyl ethyl ketone / 2-heptanone (1
/ 1 weight ratio), but the fluoropolymer according to the present invention No. 1 to No. For No. 15, good results were obtained in all tests, while No. 15 16
-No. Good results were not obtained with 19 fluoropolymers and the conventional commercially available fluorosurfactants.

[0110]

The photoresist composition according to the present invention is
A uniform coating is possible without touching the coating thickness of the photoresist composition or streaking at the time of spin coating, and the generation of particles in the liquid, which has been a problem in the past, or in the resist agent. Since there is no problem of the inclusion of bubbles in the liquid, and the problem of uneven development is eliminated due to the impediment of the wettability of the developing solution, the formation of fine resist patterns and liquid crystal patterns essential for high integration of semiconductor elements Silicon wafers for manufacturing semiconductor devices
However, even if the liquid crystal substrate has a large diameter, or even if the liquid crystal substrate has a large diameter, there is an effect that uniform coating is possible and a precise resist pattern can be formed.

Claims (3)

[Claims] 1. A photoresist comprising a copolymer of a fluorinated alkyl group-containing (meth) acrylate monomer (A) and a silicone chain-containing ethylenically unsaturated monomer (B). Composition. 2. The composition according to claim 1, which further comprises a polyoxyalkylene group-containing (meth) acrylate monomer as a copolymerization component. 3. The composition according to claim 1, further comprising a (meth) acrylate monomer having a side chain of an alkyl group having 6 or more carbon atoms as a copolymerization component.