JPH08211613A - Resist composition - Google Patents

Abstract

PURPOSE: To provide a resist compsn. having high sensitivity and high resolution by using a resin having substd. allyloxy groups as a resin binder besides a radiation-sensitive component. CONSTITUTION: This resist compsn. is a radiation-sensitive compsn. contg. a resin binder having one or more kinds of acid-unstable groups and a radiation- sensitive component which forms an acid when exposed to activated radiation. At least one of the one or more kinds of acid-unstable groups is each substd. allyloxy group having two or more substitutents. This allyloxy group having two or more substitutent bonding as an acid-unstable group to the resin binder and functioning as an acid-unstable group is decomposed by an acid formed from the radiation-sensitive component by exposure to activated radiation, a group released from the resin is a group derived from the allyloxy group and the alkali solubility of a resist is varied by the release. Since this compsn. well transmits excimer laser light or electron beams, it is suitable for use as a resist for fine working.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist composition for microfabrication of semiconductor devices, and more particularly to a pattern forming material by irradiation with deep ultraviolet ray krypton fluoride laser light, electron beam or the like.

[0002]

2. Description of the Related Art When manufacturing a semiconductor device, a resist is applied to the surface of a silicon wafer to form a photosensitive film, which is irradiated with light to form a latent image, which is then developed to form a negative or positive image. The image is obtained by the lithographic technology. By the way, as semiconductors become highly integrated, highly densified, miniaturized, and speeded up in ICs, LSIs, and VLSIs, demands for microfabrication of elements have increased, and at present, a technique for forming a micropattern of 0.5 μm or less. Is required. However, it is extremely difficult to form such a fine pattern by conventional lithography using near-ultraviolet rays or visible light, and the yield is significantly reduced. Therefore, instead of the conventional photolithography that uses near-ultraviolet light having a wavelength of 350 to 450 nm, in order to increase the resolution of exposure, far-ultraviolet light (short-wavelength ultraviolet light) having a shorter wavelength than near-ultraviolet light or a krypton fluoride laser (hereinafter ,
A lithography technique using light such as a KrF excimer laser is being studied.

In conventional lithography utilizing near-ultraviolet light, a novolac resin is widely used as a base polymer. However, since novolac resins hardly transmit light having a short wavelength such as deep ultraviolet rays and KrF excimer lasers, it is known that sufficient sensitivity cannot be obtained and the pattern shape is poor. For the purpose of improving the poor transmittance, a chemically amplified resist using a polyvinylphenol derivative as a base polymer has been studied (Japanese Patent Publication No. 27660/1990), but even if the pattern shape satisfies the requirement, I haven't arrived. Further, as a recent example, t-butoxycarbonyl group, t-amyloxycarbonyl group, t-butyl group is used as a protective group which is decomposed by an acid or a base in an alkali-soluble resin in order to improve sensitivity and heat stability. , T-hexyl group, allyl group, 2-
An example in which a cyclohexyl group or the like is bonded (JP-A-4-158)
No. 363) is known. Although the sensitivity has been considerably improved by examining the protective group in this way, further improvement is required for the more advanced required properties of the resist, particularly the resolution.

[0004]

Under the above-mentioned conventional techniques, the inventors of the present invention have earnestly studied to solve the above-mentioned problems, and as a result, when a resin having a substituted allyloxy group was used as a resin binder, high sensitivity and It was found that a high-resolution resist composition can be obtained, and the present invention has been completed based on this finding.

[0005]

Thus, according to the present invention, exposure to a resin binder having one or more acid labile groups (hereinafter sometimes simply referred to as a resin binder) (a) and activating radiation. A radiation-sensitive composition comprising a radiation-sensitive component (b) which produces an acid, wherein at least one of the acid labile groups has a substituted allyloxy group having two or more substituents (hereinafter, simply substituted). There is also provided an allyloxy group), which provides a resist composition.

The present invention will be described in detail below. The substituted allyloxy group having two or more substituents bonded as an acid labile group to the resin binder (a) used in the present invention functions as an acid labile group generally referred to in a chemically amplified resist, and Specifically, the group that is decomposed by the acid generated from the radiation-sensitive component by exposure to activating radiation and is eliminated from the resin is a group derived from a substituted allyloxy group, and the elimination of this group causes alkali solubility of the resist. It is a function that changes. Specific examples of such a substituted allyloxy group include the following formula (1)

Embedded image (In the formula, R ^{1 to} R ⁵ may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group or a substitutable vinyl group. And at least two of R ^{1 to} R ⁵ are substituents other than hydrogen atoms, R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ each independently form a ring. The number of carbon atoms in each group is 12 or less.
Is a single bond or a divalent organic group. ) The group represented by is mentioned.

Specific examples of R ^{1 to} R ^{5 in} the above formula (1) include hydrogen atom, nitro group, cyano group, chlorine atom,
Halogen atom such as bromine atom; methyl group, ethyl group, propyl group, butyl group, amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclopentyl group, 2-ethylcyclopentyl group, 1-ethylcyclohexyl group, Substitutable alkyl group such as 2-methylcyclohexyl group; vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 4-pentenyl group, hexenyl group , 2-cyclobutenyl group, 2-cyclopentenyl group, 1-methyl-2-cyclopentenyl group, 2-cyclohexenyl group, 3-methyl-2-cyclohexenyl group, etc. A dienyl group, a 1-methyl-2,4-cyclopentadienyl group,
3-methyl-2,4-cyclopentadienyl group, 3,4
-Dimethyl-2,4-cyclopentadienyl group, 2,5
-Cyclohexadienyl group, 3,5-dimethyl-2,5
-Substitutable cycloalkadienyl group such as cyclohexadienyl group; vinyl group, 1-propenyl group, 1-butene-
1-yl group, 1-buten-2-yl group, 2-butene-2
A substituted vinyl group such as an -yl group and the like. In the specific examples of the substituent, propyl represents n-propyl and isopropyl, butyl represents n-butyl, isobutyl, s-butyl and t-butyl, amyl is pentyl, 1-methylbutyl, 2-methylbutyl and 3 -Methylbutyl, 1-
Ethylpropyl, 1,1-dimethylpropyl, 1,2-
Represents dimethylpropyl and 2,2-dimethylpropyl.
Further, R ¹ and R ⁴ may be bonded to each other to form a ring such as cyclohexene or cyclopentene.
³ and R ⁵ , and R ⁴ and R ⁵ may also form a ring. However, the cyclization is not preferable because the sensitivity may decrease. Preferable examples of the substituent other than hydrogen atom of R ^{1 to} R ⁵ in the formula (1) are halogen atom and each substituent having 1 to 4 carbon atoms, particularly alkyl group having 1 to 4 carbon atoms and carbon number. 2-4 alkenyl groups are preferred.

A of the formula (1) is a single bond or a divalent organic group, and in the case of a single bond, it is the same as the above formula (1).
A preferred example of the divalent organic group is the following formula (2)

Embedded image (In the formula, B is a single bond or a divalent organic group having 1 to 10 carbon atoms, Y is a single bond, a divalent organic group having 1 to 4 carbon atoms,
-CO -, - CO ₂ -, Z is a -CO-, n
Is an integer of 0 to 3. However, when n is 1 to 3, Z bonds to an oxygen atom in the formula (1), and when n is 0, B
Binds to the oxygen atom in formula (1). ) The group represented by is mentioned.

Specific examples of the divalent organic group of B in the above formula (2) include methylene, ethylene, propane-1,
3-diyl, propane-1,2-diyl, butane-1,
4-diyl, butane-2,2-diyl, pentane-1,
5-diyl, hexane-1,6-diyl, cyclopentylene, cyclohexylene, 2-methylcyclohexylene, or other straight-chain, branched or cyclic, substitutable alkylene; vinylene, propenylene, butynylene, hexynylene, 2-
Chloropentynylene, 3-ethylcyhexenylene, cyclohexenylene, 2-chlorocyclohexenylene, -C
H = CHCH = CH -, - CH 2 C = CHCH 2 CH =
Straight chain such as CH-, -CCl = CH-CH = CCl-
In addition to branched or cyclic substitutable alkenylene, etc.

[Chemical 4] (In formula, R < ⁶ > -R < ⁸ > is a halogen atom and a C1-C4 alkyl group.), The divalent group represented by -O-, -CO.
A divalent group such as —, —CO ₂ — is bonded to —CH ₂ —O—
_{CH 2 -, - CH 2 -C} 6 H 4 -O-CH 2 -, - CH 2 -C
_{6 H 4 -CH 2 -, -} CH 2 -C 6 H 4 - or it may be in the form like. Specific examples of the divalent organic group represented by Y in the formula (2) include alkylene having 1 to 4 carbon atoms such as methylene, ethylene, vinylene, propenylene, and butynylene, and alkenylene.

Among them, preferred examples of A include, in addition to a single bond, —CH ₂ CO—, —CH (CH ₃ ) CO—, —C.
_{(CH 3) 2 CO -,} - CCl 2 CO -, - CH (Ph)
CO- (wherein (Ph) represents a phenyl group; the same applies hereinafter), -C (Ph) ₂ CO-, etc.

Embedded image (In the formula, R ⁹ and R ¹⁰ are a hydrogen atom, a halogen atom, a substitutable alkyl group, a substitutable alkenyl group, a substitutable phenyl group, or a substitutable aralkyl group, and each group has 10 carbon atoms.
It is the following. Divalent group represented by), -CH ₂ -C ₆ H _{4
-O-CH 2 CO -, -} CH (C 2 H 3) -C 6 H 4 -O-
_{CH 2 CO -, - CH 2} - (C 6 H 3 (CH 3)) - O-C
_{H (CH 3) CO -,} - CHCl-C 6 H 4 -O-CH 2 C
The following formula (5) such as O-

[Chemical 6] (In the formula, R ^{11 to} R ¹⁶ are a hydrogen atom, a halogen atom, a substitutable alkyl group and a substitutable alkenyl group, and each group has 4 or less carbon atoms.) And the like. is there.
Specific examples of the substituents of the formulas (4) and (5) include the same as R ^{1 to} R ⁵ of the formula (1) for the halogen atom, the substitutable alkyl group and the substitutable alkenyl group, Examples of the substitutable aralkyl group include benzyl group, 4-hydroxybenzyl group, 4-methylbenzyl group, phenethyl group, 3-methylphenethyl group, 2,4,6-trimethylphenethyl group and 4-hydroxyphenethyl group.

The substituted allyloxy group of the present invention has 2 substituents.
As described above, those which are both substituents (1,1-di-substituted product) are most preferable in order to achieve higher sensitivity and resolution, and then the substituents at the 1-position are both hydrogen atoms. (1-position non-substituted product) and one having only one substituent at the 1-position (1-position mono-substituted product). That is, in the above formula (1), it is most preferable that both R ¹ and R ² are substituents.

Preferred specific examples of the substituted allyloxy group of the present invention include groups represented by the above formula (1) such as the following formulas (1-a) to (1-j).

[Chemical 7]

Embedded image

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

Embedded image

[Chemical 15]

Embedded image

The resin binder (a) used in the present invention contains at least a phenol derivative such as a novolac resin, a partially hydrogenated novolac resin, or a copolymer of a phenol derivative with a styrene derivative or another phenol derivative as a raw material. A phenolic resin or a partially hydrogenated product thereof; at least a vinylphenol derivative such as a polyvinylphenol resin, a partially hydrogenated polyvinylphenol resin, a copolymer of a vinylphenol derivative with a styrene derivative or another vinylphenol derivative, etc. Vinylphenol resin or a partially hydrogenated product thereof, which is prepared from at least a (meth) acrylic acid derivative such as a copolymer of a (meth) acrylic acid derivative and a styrene derivative or a vinylphenol derivative (meth). ) Acrylic acid derivative resin; poly A vinyl alcohol-based resin containing at least vinyl alcohol as a raw material, such as a copolymer of a nyl alcohol derivative and a styrene derivative, and the like, and the method for producing the resin binder is not particularly limited. , (1) a method of introducing a substituted allyloxy group by a conventional method after synthesizing a resin as a raw material having no substituted allyl group (hereinafter sometimes referred to as a base resin), (2) introducing a substituted allyloxy group in advance Examples of the method include anion polymerization, cationic polymerization, and radical polymerization of the prepared monomer alone or together with other monomers.

In the method (1), the substituted allyloxy group is introduced by subjecting the substituted allyl ester of a halogenated carboxylic acid corresponding to the desired substituted allyloxy group to a condensation reaction with the hydroxyl group of the resin under basic conditions. Method etc. are mentioned. In the method (2), when performing cationic polymerization, the reaction is usually performed at a low temperature. The molecular weight of the resin binder (a) obtained by these methods is not particularly limited, but from the viewpoint of resolution, the upper limit is preferably 100,000, more preferably 20,000, and the film-forming property is From the point, the lower limit is preferably 1,000, more preferably 2,000. In addition, a resin having a substituted allyloxy group introduced therein in a proportion of usually 1 to 99%, preferably 5 to 70%, more preferably 10 to 60%, and further preferably 15 to 55% based on all structural units is a resin. Used as a binder. Further, an acid labile group other than the substituted allyloxy group (hereinafter, may be referred to as other acid labile group)
For example, a t-butyloxy group and a t-butyloxycarbonyl group described in JP-B-2-27660, JP-B-5
Examples include isopropyloxycarbonyl group described in JP-A-19139 and t-amyloxycarbonyl group described in JP-A-4-158363.

As the monomer having a substituted allyloxy group used for polymerizing the resin by the above-mentioned method, for example, a hydrogen atom of a hydroxyl group of vinylphenol such as a substituted allyloxystyrene compound is substituted with a substituted allyl group. Compound, a substituted allyloxycarbonyloxystyrene compound or a substituted allyloxycarbonylalkyloxystyrene compound, the hydrogen atom of the hydroxyl group of vinylphenol or the carboxyl group of (meth) acrylic acid is represented by the above general formula (1) and A is two. Examples include compounds substituted with a substituted allyloxy group (group containing a substituted allyloxy group) that is a valent organic group, such as vinylphenol derivatives and (meth) acrylic acid derivatives into which a substituted allyloxy group has been introduced. Substitution by substitution with other monomers by conventional method Obtaining the resin binder having a group. Further, examples of the other monomer copolymerizable with these monomers include a monomer represented by the following formula (6).

[Chemical 17] (In the formula (6), R ¹⁷ is a hydrogen atom, a substituted alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or a nitro group, and R ¹⁸ and R ¹⁹ are each independently a hydrogen atom or a hydroxyl group. , A carboxyl group, a halogen atom, and a substitutable alkyl group having 1 to 5 carbon atoms.) Styrene, α-methylstyrene, 4-methylstyrene,
4-methoxystyrene, 4-t-butoxystyrene, 4
Substituteable styrenes such as -t-amyloxystyrene and 4-hydroxystyrene are preferable examples because they are easily available and easily synthesized.

Among the resin binders obtained by any method such as the above-mentioned methods (1) and (2), polyvinylphenol resin, partially hydrogenated polyvinylphenol resin, vinylphenol derivative and (meth) acryl. Copolymers with acid derivatives are preferred, especially poly-p
-Vinylphenol resin, partially hydrogenated poly-p-vinylphenol resin, and a copolymer of a p-vinylphenol derivative and a (meth) acrylic acid derivative are preferable. In the copolymer of vinylphenol-based resin binders, the ratio of structural units derived from vinylphenols is 99% or less with respect to the whole copolymer, and the lower limit is usually 5% or more, preferably 15% or more. , And more preferably 25% or more. In addition, the hydrogenation rate in the case of using a hydrogenated vinylphenol resin is usually 50% as an upper limit, preferably 35%, more preferably 20% as a lower limit with respect to an aromatic unsaturated bond in the resin, and usually a lower limit. It is in the range of 1%, preferably 3%, more preferably 5%. When a (meth) acrylate resin binder is used, the ratio of the structural unit derived from the (meth) acrylic acid derivative to the structural unit derived from the other monomer is 90:10 to 10:90, preferably 75:25. ~
It is 25:75. Of course, in such a copolymer,
The structural unit into which the substituted allyloxy group is introduced is not only the structural unit derived from the (meth) acrylic acid derivative, but also the (meth)
It may be a structural unit derived from a monomer other than the acrylic acid derivative.

The radiation-sensitive component (b) used in the present invention is not particularly limited as long as it is a substance capable of generating a Bronsted acid or a Lewis acid (hereinafter referred to as PAG) when exposed to activating radiation, and the onium is not limited. Salts, halogenated organic compounds, quinonediazide compounds, α, α-bis (sulfonyl) diazomethane compounds, α-carbonyl-α
-Sulfonyldiazomethane compounds, sulfone compounds,
Known compounds such as organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds can be used. Examples of onium salts include diazonium salts, ammonium salts, iodonium salts such as triphenyliodonium triflate, sulfonium salts such as triphenylsulfonium triflate, phosphonium salts, arsonium salts, oxonium salts and the like. Examples of the halogenated organic compound include a halogen-containing oxadiazole compound, a halogen-containing triazine compound, a halogen-containing acetophenone compound, a halogen-containing benzophenone compound, a halogen-containing sulfoxide compound, a halogen-containing sulfone compound, and a halogen-containing thiazole compound. , Halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, other halogen-containing heterocyclic compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, sulfenyl halide compounds and the like. The
Specifically, tris (2,3-dibromopropyl) phosphate, tris (2,3-dibromo-3-chloropropyl) phosphate, tetrabromochlorobutane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromo Biphenyl, allyltribromophenyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, tetrachlorobisphenol A bis (chloroethyl) ether, tetrabromobisphenol A bis (bromoethyl) ether, bisphenol A bis (2,3-dichloro) Propyl) ether, bis (2,3-dibromopropyl) ether of bisphenol A, bis (2,3-dichloropropyl) ether of tetrachlorobisphenol A, tetrabromobisphine Bis Nord A (2,3-dibromopropyl) ether, tetrachloro bisphenol S,
Tetrabromobisphenol S, bis (chloroethyl) ether of tetrachlorobisphenol S, bis (bromoethyl) ether of tetrabromobisphenol S,
Bisphenol S bis (2,3-dichloropropyl)
Ether, bis (2,3-dibromopropyl) ether of bisphenol S, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2 Halogen-based flame retardants such as bis (4- (2-hydroxyethoxy) -3,5-dibromophenyl) propane, dichlorodiphenyltrichloroethane, pentachlorophenol, 2,4,6-trichlorophenyl 4-nitrophenyl ether, 2 , 4-dichlorophenyl 3'-methoxy-4'-nitrophenyl ether, 2,4-dichlorophenoxyacetic acid, 4,5,6,7-tetrachlorophthalide, 1,1-bis (4-chlorophenyl) ethanol, 1 , 1-bis (4-chlorophenyl) -2,2,2
Examples thereof include organic chloro-based pesticides such as trichloroethanol, 2,4,4 ′, 5-tetrachlorodiphenyl sulfide and 2,4,4 ′, 5-tetrachlorodiphenyl sulfone.

Specific examples of the quinonediazide compound include:
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid ester Ester, 2,1-benzoquinonediazide-5
Sulfonic acid ester of quinonediazide derivative such as sulfonic acid ester, 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-
Sulfonic acid of quinonediazide derivative such as naphthoquinone-2-diazide-5-sulfonic acid chloride, 1,2-naphthoquinone-1-diazide-6-sulfonic acid chloride and 1,2-benzoquinone-1-diazide-5-sulfonic acid chloride Examples include chloride. As the α, α-bis (sulfonyl) diazomethane compound, an unsubstituted, symmetrically or asymmetrically substituted alkyl group,
Examples include α, α-bis (sulfonyl) diazomethane having an alkenyl group, an aralkyl group, an aromatic group, or a heterocyclic group. Specific examples of the α-carbonyl-α-sulfonyldiazomethane compound include an α- having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, or heterocyclic group. Carbonyl-α-sulfonyldiazomethane and the like can be mentioned. Specific examples of the sulfone compound include a sulfone compound having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, or heterocyclic group, a disulfone compound, and the like. Examples of the organic acid ester include carboxylic acid ester, sulfonic acid ester, and phosphoric acid ester, and examples of the organic acid amide include carboxylic acid amide, sulfonic acid amide, and phosphoric acid amide.
Examples of the organic acid imide include carboxylic acid imide, sulfonic acid imide, and phosphoric acid imide.

These PAGs may be used alone or in combination of two or more. The blending amount of these PAGs is usually 0.01 part by weight, preferably 0.2 part by weight, with respect to 100 parts by weight of the resin used in the present invention.
The upper limit is usually 50 parts by weight, preferably 30 parts by weight.
If it is less than 0.01 parts by weight, it becomes impossible to form a pattern. If the amount exceeds 50 parts by weight, problems such as easy occurrence of undeveloped residue and deterioration of pattern shape occur, and in any case, it is not preferable in terms of resist performance.

In the present invention, the resist composition comprising the resin and PAG is used by dissolving it in a solvent. As the solvent, those generally used as a solvent for a resist composition can be used, and specific examples thereof include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cyclopentanone, cyclohexanone; n-propanol. , I-propanol, n-
Alcohols such as butanol, i-butanol, t-butanol, cyclohexanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane; ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono Alcohol ethers such as ethyl ether; Esters such as propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate; 2-
Oxycarboxylic acid esters such as methyl oxypropionate, ethyl 2-oxypropionate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate; cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate. Propylene glycols such as propylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, etc .; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc. The di Tylene glycols; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; polarities such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylacetamide, N-methylpyrrolidone Examples thereof include solvents, and these may be used alone or in combination of two or more.

In the present invention, those which are generally added to the resist composition as additives, for example, surfactants, storage stabilizers, sensitizers, anti-striation agents and the like, which are compatible with each other, are added. You can

The resist composition of the present invention usually uses an aqueous alkali solution as a developing solution. Specific examples thereof include aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate and ammonia; ethylamine,
Aqueous solution of primary amines such as propylamine; Aqueous solution of secondary amines such as diethylamine and dipropylamine;
Aqueous solutions of tertiary amines such as trimethylamine and triethylamine; Aqueous solutions of alcohol amines such as diethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide , An aqueous solution of a quaternary ammonium hydroxide such as trimethyl hydroxyethyl ammonium hydroxide. Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a resin dissolution inhibitor, or the like can be added to the alkaline aqueous solution.

The resist composition of the present invention contains the above-mentioned resin and acid generator and, if necessary, additives, and is usually dissolved in a solvent to be used as a resist composition solution. . For example, a resist film can be formed by applying this solution to the surface of a substrate such as a silicon wafer by a conventional method, and then removing the solvent by drying. As the application method at this time, spin coating is particularly preferred. It The exposure for pattern formation is performed by irradiating the resist film with deep ultraviolet ray, KrF excimer laser, or electron beam, and further heat treatment (post-exposure bake) can further increase the sensitivity.

The preferred embodiments of the present invention are shown below. Resin binder (a) comprising a resin having a substituted allyloxy group having two or more substituents as an acid labile group
A radiation-sensitive composition comprising a radiation-sensitive component (b) which produces an acid when exposed to activating radiation, wherein the substituted allyloxy group of the resin binder (a) is the 1-position mono-substituted product or 1 A resist composition, which is a non-position-substituted product. A radiation-sensitive composition comprising a resin binder (a) and a radiation-sensitive component (b) which produces an acid when exposed to activating radiation, the resin binder (a) having the formula (1):

(In the formula, R ^{1 to} R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a nitro group, a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group, a substitutable vinyl group. And R ¹ and R ⁴ , R ³ and R ⁵ , R ⁴
And R ⁵ may independently form a ring. Each group has 12 or less carbon atoms. At least two of these are substituents other than hydrogen atoms. Also R
^{When 1} is a hydrogen atom, R ² is also a hydrogen atom. A is a single bond or a divalent organic group. ) A resin composition having a substituted allyloxy group represented by:

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Parts and% in each example are based on weight unless otherwise specified.

Reference Example 1 3-Methyl-2-butenyl
Synthesis of bromoacetate 4-methyl-2-buten-1-ol 43.9 g (0.
51 mol), triethylamine 51.6 g (0.51)
mol) and 300 ml of dichloromethane were charged into a 1-liter flask and cooled to 0 ° C. While stirring the mixture at 0 ° C., 100.9 g of bromoacetyl bromide (0.5
(0 mol) was added dropwise over 1 hour, and stirring was continued at room temperature for 3 hours. The solid content was filtered from the obtained reaction solution, and 3
After washing with water twice and distilling, 66.5 g of 3-methyl-2-butenyl bromoacetate was obtained.

Reference Example 2 1-Methyl-2-butenyl
Synthesis of bromoacetate By the same method as in Reference Example 1 except that 43.9 g (0.51 mol) of 3-penten-2-ol was used instead of 3-methyl-2-buten-1-ol, 48.5 g of 1
-Methyl-2-butenyl bromoacetate was obtained.

Reference Example 3 Synthesis of 1,1-dimethyl-2-pentenyl bromoacetate 43.9 g of 2-methyl-3-buten-2-ol instead of 3-methyl-2-buten-1-ol 0.51m
2) by the same method as in Reference Example 1, except that
5.4 g of 1,1-dimethyl-2-propenyl bromoacetate was obtained.

Reference Example 4 Synthesis of 3-cyclohexenyl bromoacetate 50.0 g (0.51 mo) of 2-cyclohexen-1-ol instead of 3-methyl-2-buten-1-ol
1) except that the same method as in Reference Example 1 was used.
4 g of 3-cyclohexenyl bromoacetate was obtained.

Reference Example 5 3-Methyl-2-butenyl
Synthesis of 4- (bromomethyl) phenoxyacetate 20.7 g (0.10 mol) of 3-methyl-2-butenyl bromoacetate obtained in Reference Example 1 and 12.4 g (0.10 mo) of 4-hydroxybenzyl alcohol
l), 15.2 g of anhydrous potassium carbonate (0.11 mo
l), potassium iodide 18.3 g (0.11 mol),
Charge 150 ml of acetone into a 500 ml flask,
Refluxed for 7 hours with stirring. The solid content is filtered from the obtained reaction solution, washed with water three times, and then concentrated to give 3-methyl-2-.
24.0 g of butenyl 4- (hydroxymethyl) phenoxy) acetate was obtained. Next, 24.0 g (0.096 mol) of the acetate obtained here, 20.6 g (0.20 ml) of sodium bromide, and 9.4 g (0.
12 mol) and dimethylformamide 150 ml to 50
It was charged into a 0 ml flask and cooled to 0 ° C. This is 0
13.7g of mesyl chloride while stirring at ℃
(0.12 mol) was added dropwise over 1 hour, and then 0 ° C.
The stirring was continued for 6 hours. The solid content was filtered from the obtained reaction solution, washed three times with water, concentrated, and then subjected to column chromatography (elution solvent: n-hexane / ethyl acetate = 10/1) to give 3-methyl-2-butenyl 4. 1-1.8 g of-(bromomethyl) phenoxyacetate was obtained.

Reference Example 6 Synthesis of 1,1-dimethyl-2-propenyl (4-bromomethyl) phenoxyacetate 1,1-Dimethyl-obtained in Reference Example 3 instead of the ester obtained in Reference Example 1 10.9 g of 1,1-dimethyl-2-propenyl (4-bromomethyl) phenoxyacetate was obtained by the same method as in Reference Example 5 except that 20.7 g (0.10 mol) of 2-propenyl bromoacetate was used.

Reference Example 7 3-Methyl-2-butenyl
Chloro oxalate Oxalyl chloride 25.4 g (0.20 mol),
250 ml of n-heptane was charged into a 1-liter eggplant-shaped flask, and 3-methyl-2-buten-1-ol 21.5 (0.25mo) was added while bubbling nitrogen at room temperature.
1) is added dropwise over 3 hours, and stirring is continued for another 2 hours. After that, the reaction solution is concentrated and distilled to perform 11.6 g.
To give 3-methyl-2-butenyl chlorooxalate.

Reference Example 8 Synthesis of 2-butenyl bromoacetate Reference was made except that 36.8 g (0.51 mol) of 2-buten-1-ol was used instead of 3-methyl-2-buten-1-ol. By the same method as in Example 1, 50.2 g of 2-
Butenyl bromoacetate was obtained.

Reference Example 9 Synthesis of 1-methyl-2-propenyl bromoacetate 36.8 g (0.51 mol) of 3-buten-2-ol was used instead of 3-methyl-2-buten-1-ol. Otherwise, by the same method as in Reference Example 1 27.2 g of 1-
Methyl-2-propenyl bromoacetate was obtained.

(Synthesis Example 1) 3-Methyl-2-butenyloxycarbonylmethyl hydrogenated polyvinylphenol 10% Hydrogenated polyvinylphenol 12.0 g (Mw
= 4,950), 5 ml of 100 ml of dimethylformamide
A 00 ml flask was charged and dissolved. Here, 6.2 g (0.03 mol) of 3-methyl-2-butenyl bromoacetate obtained in Reference Example 1 and anhydrous potassium carbonate 6.9.
g (0.05 mol), potassium iodide 8.3 g (0.
(05 mol) was added and the mixture was stirred at 50 ° C. for 8 hours. Then, the reaction solution was cooled, poured into water, and the deposited precipitate was filtered off. The precipitate was washed with 0.1% hydrochloric acid and water three times, and dried to obtain 13.1 g of 3-methyl-2-butenyloxycarbonylmethyl hydrogenated polyvinylphenol. The obtained resin has a Mw =
It was 6,310. When this resin was analyzed by ¹ H-NMR spectrum, the modification ratio of hydroxyl groups was 26%.

Synthesis Example 2 Synthesis of 1-methyl-2-butenyloxycarbonylmethyl hydrogenated polyvinylphenol 1-methyl-2-obtained in Reference Example 2 instead of the ester obtained in Reference Example 1 Butenyl bromoacetate 6.
11.8 g of 1-methyl-2-butenyloxycarbonylmethyl hydrogenated polyvinylphenol was obtained in the same manner as in Synthesis Example 1 except that 2 g (0.03 mol) was used. The obtained resin has a Mw =
It was 6,270. When this resin was analyzed by ¹ H-NMR spectrum, the modification ratio of hydroxyl groups was 25%.

(Synthesis Example 3) 1,1-Dimethyl-2-propenyloxycarbonylmethyl hydrogenated polyvinylphenol 1,1-Dimethyl-2 obtained in Reference Example 3 instead of the ester obtained in Reference Example 1 -Propenyl Bromoacetate By the same method as in Synthesis Example 1 except that 6.2 g (0.03 mol) was used, 12.2 g of 1,1-dimethyl-
2-Propenyloxycarbonyl hydrogenated polyvinylphenol was obtained. As a result of GPC analysis, the obtained resin was Mw = 6,290. Further, the resin ¹ H
As a result of analysis by -NMR spectrum, the modification ratio of hydroxyl groups was 26%.

(Synthesis Example 4) 3-Cyclohexenyloxycarbonylmethyl hydrogenated polyvinylphenol 6.6 g of 3-cyclohexenyl bromoacetate obtained in Reference Example 4 instead of the ester obtained in Reference Example 1.
By the same method as in Synthesis Example 1 except that (0.03 mol) was used, 10.9 g of 2-cyclohexenyloxycarbonylmethyl hydrogenated polyvinylphenol was obtained.
As a result of GPC analysis, the obtained resin was Mw = 6,340.
Met. When this resin was analyzed by ¹ H-NMR spectrum, the modification ratio of hydroxyl groups was 25%.

(Synthesis Example 5) 4- (3-Methyl-2-butenyloxycarbonylmethyloxy) benzylated hydrogenated polyvinylphenol In place of the ester obtained in Reference Example 1, 2-obtained in Reference Example 5 was used. Methyl-2-butenyl 4- (bromomethyl)
17.4 g of 4 was prepared in the same manner as in Synthesis Example 1 except that 9.4 g (0.03 mol) of phenoxyacetate was used.
-(3-Methyl-2-butenyloxycarbonylmethyloxy) benzylated hydrogenated polyvinylphenol was obtained. As a result of GPC analysis, the obtained resin was Mw = 7.5.
It was 10. When this resin was analyzed by ¹ H-NMR spectrum, the modification ratio of hydroxyl groups was 25%.

(Synthesis Example 6) 4- (1,1-dimethyl-2)
-Propenyloxycarbonylmethyloxy) benzyl hydrogenated polyvinylphenol 1,1-dimethyl-2-propenyl-4- (bromomethyl) phenoxyacetate obtained in Reference Example 6 instead of the ester obtained in Reference Example 1. 4g (0.03mo
17) by the same method as in Synthesis Example 1 except that 1) is used.
2 g of 4- (1,1-dimethyl-2-propenyloxycarbonylmethyloxy) benzylated hydrogenated polyvinylphenol was obtained. As a result of GPC analysis, the obtained resin was Mw = 7,420. Further, the resin ¹ H
As a result of analysis by -NMR spectrum, the modification ratio of hydroxyl groups was 24%.

(Synthesis Example 7) 3-Methyl-2-butenyloxycarbonylmethylated polyvinylphenol 12.0 g of polyvinylphenol (Mw = 4,800) was used instead of 10% hydrogenated polyvinylphenol. By the same method as in Synthesis Example 1, 12.1 g of 3-methyl-2-butenyloxycarbonylmethylated polyvinylphenol was obtained. As a result of GPC analysis, the obtained resin was Mw = 6,220. When this resin was analyzed by ¹ H-NMR spectrum, the modification ratio of hydroxyl groups was 28%.

(Synthesis Example 8) 3-Methyl-2-butenyloxycarbonylcarbonylated polyvinylphenol Polyvinylphenol (Mw = 4,800) 12.0
g, 100 ml of THF was charged into a 300 ml eggplant-shaped flask, and after dissolution, 10.1 g of triethylamine (0.1 m
ol) is added. This solution was cooled to 0 ° C., 12.4 g (0.07 mol) of 3-methyl-2-butenyl chlorooxalate obtained in Reference Example 7 was added dropwise over 1 hour with stirring, and then further 0 ° C. The stirring was continued for 3 hours. After completion of the reaction, the precipitate in the reaction solution was removed by filtration, poured into a 3% aqueous sodium hydrogen carbonate solution, and the precipitate was filtered off. This precipitate was diluted with 0.1% hydrochloric acid and water to 3 times each.
After washing each time and vacuum drying, 15.9 g of 3-methyl-2 was used.
-Butenyloxycarbonylcarbonylated polyvinylphenol was obtained. As a result of GPC analysis, the obtained resin was Mw = 6,420. Further, the resin ¹ H
As a result of analysis by -NMR spectrum, the modification ratio of hydroxyl groups was 31%.

(Synthesis Example 9) 3-Methyl-2-butenyloxycarbonylated polyvinylphenol Polyvinylphenol (Mw = 4,800) 12.0
g, and 200 ml of THF were charged into a 500 ml eggplant-shaped flask, and after dissolution, 9.1 g of triethylamine (0.09 m
ol) was added and the mixture was cooled to -30 ° C. Here, 7.4 g of 3-methyl-2-butenyl chloroformate (0.05
(mol) was added dropwise at -30 ° C over 1 hour, and after the addition, stirring was further performed at -30 ° C for 5 hours. Then, the reaction solution was poured into a 3% aqueous solution of sodium hydrogen carbonate, and the deposited precipitate was separated by filtration. The precipitate was washed with 0.1% hydrochloric acid and water three times, and dried to obtain 13.8 g of 3-methyl-2-butenyloxycarbonylated polyvinylphenol. As a result of GPC analysis, the obtained resin was Mw = 6,09.
It was 0. When this resin was analyzed by ¹ H-NMR spectrum, the modification ratio of hydroxyl groups was 29%.

(Synthesis Example 10) 3-Methyl-2-butenylated polyvinylphenol Polyvinylphenol (Mw = 4,800) 12.0
g and 100 ml of acetone were placed in a 300 ml eggplant-shaped flask and dissolved. After dissolution, 11.9 g (0.08) of 1-bromo-3-methyl-2-butene (manufactured by Tokyo Kasei).
mol), anhydrous potassium carbonate 15.2 g (0.11 mo)
1) and 18.3 g (0.11 mol) of potassium iodide were added, and the mixture was refluxed for 6 hours. After cooling the reaction solution, salts were filtered and poured into 5 liters of water. The resulting precipitate was filtered and dried to obtain 13.7 g of 3-methyl-2-butenylated polyvinylphenol. As a result of GPC analysis, the obtained resin was Mw = 5,660. When this resin was analyzed by ¹ H-NMR spectrum, the modification ratio of hydroxyl groups was 32%.

(Synthesis Example 11) 4-hydroxystyrene /
3-methyl-2-butenyl methacrylate copolymer 4-hydroxystyrene (p-vinylphenol) 7
2.1 g (0.60 mol), 3-methyl-2-butenyl methacrylate 92.5 g (0.60 mol), azobisbutyronitrile 1.5 g (0.009 mol),
300 ml of dioxane was placed in a 1-liter eggplant-shaped flask and stirred at 80 ° C. for 20 hours under a nitrogen stream.
The obtained reaction liquid was put into 5 liters of xylene, and the generated precipitate was filtered. The solid content obtained is 300 m of acetone
It was dissolved in 1 and poured into 4 liters of n-hexane, and the generated precipitate was filtered (reprecipitation operation). This reprecipitation operation was repeated 3 times and then dried to obtain 103.5 g of 4-hydroxystyrene / 3-methyl-2-butenyl methacrylate copolymer. As a result of GPC analysis, the obtained copolymer was Mw = 8,800. Further, the resin ¹ H
-When analyzed by NMR spectrum, the copolymerization ratio was
4-hydroxystyrene / 3-methyl-2-butenyl
Methacrylate = 53/47.

(Synthesis Example 12) 2-butenyloxycarbonylmethyl hydrogenated polyvinylphenol In place of the ester obtained in Reference Example 1, 5.8 g (0.0 g) of 2-butenyl bromoacetate obtained in Reference Example 8 was obtained.
12.8 g of 2-butenyloxycarbonylmethyl hydrogenated polyvinylphenol was obtained by the same method as in Synthesis Example 1 except that 3 mol) was used. As a result of GPC analysis, the obtained resin was Mw = 6,250. When this resin was analyzed by ¹ H-NMR spectrum, the modification ratio of hydroxyl groups was 28%.

(Synthesis Example 13) Synthesis of 1-methyl-2-propenyloxycarbonylmethyl hydrogenated polyvinylphenol 1-methyl-2-propenyl obtained in Reference Example 9 instead of the ester obtained in Reference Example 1 Synthetic Example 1 except that 5.8 g (0.03 mol) of bromoacetate was used.
12.5 g of 1-methyl-2-propenyloxycarbonylmethyl hydrogenated polyvinylphenol was obtained in the same manner as in. The obtained resin was analyzed by GPC,
Mw = 6,200. Further, the resin ¹ H-N
When analyzed by MR spectrum, the modification ratio of hydroxyl group is 2
7%.

(Synthesis Example 14) 2-Propenylated polyvinylphenol In the same manner as in Synthesis Example 10 except that 9.7 g (0.08 mol) of allyl bromide was used instead of 1-bromo-3-methyl-2-butene. 13.1 g of 2-propenylated polyvinylphenol was obtained. The obtained resin is GPC
As a result of the analysis, Mw was 5,440. When this resin was analyzed by ¹ H-NMR spectrum, the modification ratio of hydroxyl groups was 36%.

(Examples 1 to 11 and Comparative Examples 1 to 3) 100 parts of each resin obtained in Synthesis Examples 1 to 14 (Systems using Synthesis Examples 1 to 11 are Examples 1 to 11) The systems using the resins of 12 to 14 are Comparative Examples 1 to 3), 5 parts of triphenylsulfonium triflate as a photoacid generator,
Fluorine-based surfactant 0.01 part of ethyl lactate 44
It was dissolved in 0 part and filtered through a 0.1 μm polytetrafluoroethylene filter (manufactured by Millipore) to prepare a resist solution. Each of these resist solutions was spin-coated on a silicon wafer and then baked at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. This wafer is an excimer stepper (NA
= 0.45) and a test reticle were used for exposure. Then, the wafers coated with the resist solutions containing the resins of Synthesis Examples 12 to 14 are baked at 110 ° C. for 60 seconds, and the wafers using the resin coated resist solutions of Synthesis Examples 1 to 11 are baked at 90 ° C. It was baked for 60 seconds. Then, each wafer was immersed in a tetramethylammonium hydroxide aqueous solution for 1 minute to obtain a positive pattern. The sensitivity and resolution of the obtained resist film were as shown in Table 1.

[0050]

[Table 1]

No pattern was obtained with the composition containing the resin binder having an unsubstituted allyloxy group (Comparative Example 3).
It could not be used as a resist. In particular, in the systems in which the number of substituents of the substituted allyloxy group of the resin binder is 2 or more (Examples 1 to 11), the system having one substituent (Comparative Examples 1 and 2)
Even though the baking temperature during exposure is lower (weak exposure conditions), high sensitivity is exhibited. As described above, it was found that the composition of the present invention provided excellent properties as a resist.

(Embodiment 12) Embodiments 3 and 11
Each resist composition was spin-coated on a silicon wafer and then baked at 90 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. Excimer stepper (NA = 0.4
5) and a test reticle are used for exposure and development.
A line and space (L / S) pattern of μm was obtained. Each pattern was subjected to a heat resistance test with a 500 mW low-pressure mercury lamp in the presence or absence of UV cure at 90 ° C. for 1 minute, and the heat resistance temperature was as shown in Table 2. The heat-resistant temperature in the table is the temperature at which the pattern edge begins to deform after processing for 5 minutes on the hot plate at the set temperature.

[0053]

[Table 2]

[0054]

As described above, according to the present invention, a resist composition having excellent resist characteristics such as sensitivity and resolution can be obtained.
Furthermore, since the resist composition of the present invention sufficiently transmits short-wavelength light such as far-ultraviolet light and KrF excimer laser light and an electron beam, it is possible to obtain a finely processed semiconductor element.

Claims (3)

[Claims] 1. A radiation-sensitive composition comprising a resin binder (a) having one or more acid labile groups and a radiation-sensitive component (b) which produces an acid when exposed to activating radiation. A resist composition, wherein at least one of the acid labile groups is a substituted allyloxy group having 2 or more substituents. 2. A radiation-sensitive composition comprising a resin binder (a) having one or more acid labile groups and a radiation-sensitive component (b) which produces an acid when exposed to activating radiation. At least one of the acid labile groups is a substituted allyloxy group having 2 or more substituents, and the resin binder (a) is a phenolic resin or a partial hydrogenated product thereof, a vinylphenolic resin or a partial thereof. A resist composition comprising a hydrogenated product or a (meth) acrylic acid-based resin. 3. A substituted allyloxy group is represented by the following formula (1): (In the formula, R ^{1 to} R ⁵ may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group or a substitutable vinyl group. And at least two of R ^{1 to} R ⁵ are substituents other than hydrogen atoms, R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ each independently form a ring. The number of carbon atoms in each group is 12 or less.
Is a single bond or a divalent organic group. 3. The resist composition according to claim 1, which is a group represented by