JPH08194308A - Resist composition - Google Patents

Abstract

PURPOSE: To obtain a resist compsn. excellent in various characteristics of a resist such as sensitivity and resolution by preparing a radiation sensitive compsn. contg. a resin binder, a radiation sensitive component which produces an acid when exposed to activating radiation and a specified compd. and using a compd. having a substd. allyloxy group having one or more substituents as the specified compd. CONSTITUTION: This resist compsn. is a radiation sensitive compsn. contg. a resin binder, a radiation sensitive component which generates an acid when exposed to activated radiation and a specified compd. having a substd. allyloxy group having one or more substituents represented by the formula, wherein each of R<1> -R5<5> is H, halogen, nitro, cyano, etc., at least one of R<1> -R<5> is a substituent other than H, R<1> and R<4> , R<3> and R<5> , or R<4> and R<5> may form a ring and each group is a <=12C group.

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 beam, electron beam or the like, and obtained by it. The present invention relates to a method of improving thermal characteristics of a resist pattern.

[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.

However, when short-wavelength ultraviolet light or KrF excimer laser light is used, since the photosensitive wavelength range is limited in the system using the conventional orthoquinonediazide compound, the exposure wavelength is changed to a single wavelength for the purpose of improving resolution. The problem has arisen that it cannot be simply applied to. Therefore, in recent years, for the purpose of high sensitivity and high resolution, a compound that generates an acid upon irradiation with activating radiation such as light or electron beam and a compound that decomposes with an acid catalyst and is solubilized in a developing solution are used. The combined resist system is drawing attention. For example, an acetal compound (JP-A-48-89003), an enol ether compound (JP-A-55-12995), and the like are disclosed as compounds to be combined with a compound that generates an acid upon irradiation with light (photo-acid generator). There is. Further, in a resist composition using a resin binder that decomposes with an acid catalyst and is solubilized in a developing solution, a composition in which a polymer having an orthoester group in the main chain is the resin binder (JP-A-56-17345) ), A composition having a tert-butyl ester of carboxylic acid or a polymer having a tert-butyl carbonate group of phenol as a resin binder (Japanese Patent Publication No. 27660/1990). However, these are sensitivity, storage stability, stability over time, resolution,
It was not completely satisfactory in terms of pattern shape.

Further, as a recent example, a t-butoxycarbonyl group is used as a protecting group which is decomposed by an acid or a base in an alkali-soluble resin in order to improve sensitivity and heat stability.
Examples in which a t-amyloxycarbonyl group, a t-butyl group, a t-hexyl group, an allyl group, a 2-cyclohexyl group and the like are bound (JP-A-4-158363) and tert in the molecule
-Examples using a compound having an amyl ester structure (JP-A-4-269754) are disclosed. Although the characteristics are improved by such examination, further improvement is required for the more advanced required characteristics of the resist, particularly the resolution.

In addition, since the resist film using any of the above resist compositions is far from the practical level in terms of thermal stability, it is generated in the etching step when transferring the resist pattern to the substrate (for example, silicon substrate). There is a problem that the shape of the resist is deteriorated by heat and the resist shape cannot be accurately transferred to the substrate. With regard to this problem, by using a group that forms upon cleavage the second carbonium ion intermediate having a proton available for the reaction as a protective group that is decomposed by an acid or a base in an alkali-soluble resin, A composition having improved thermal stability (heat resistance) is disclosed (JP-A-5-19139). However, for example, when compared with a resist having a t-butyl group as a substituent of an acid labile group, the thermal properties of the resist film described in the above publication are improved, but the sensitivity required for the resist film is significantly inferior. It is not practical.

As described above, in the present technology, a resist composition showing excellent resist characteristics in a well-balanced manner has not been obtained in the technique of forming a resist pattern using short-wavelength ultraviolet light or KrF excimer laser light.

[0007]

Under the circumstances, the inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, when a specific compound having a substituted allyloxy group was used, high sensitivity and high resolution were obtained. To obtain a resist composition,
In addition, it has been found that the thermal characteristics can be significantly improved by subjecting the resist pattern formed by the resist composition to actinic radiation irradiation, and the present invention has been completed based on this finding.

[0008]

The invention thus comprises a resin binder (a), a radiation-sensitive component (b) which produces an acid when exposed to activating radiation and a specific compound (c). A resist composition, which is a radiation-sensitive composition, wherein the specific compound (c) is a compound containing a substituted allyloxy group having one or more substituents.

The present invention will be described in detail below. Resin Binder (a) The resin binder (a) used in the present invention is a resin that is soluble in an alkali developing solution, or a resin that has an acid labile group and can be dissolved in an alkali developing solution by its decomposition. Anything can be used if it exists. For example, novolak resin, partially hydrogenated novolac resin, polyhydroxystyrene, partially hydrogenated polyhydroxystyrene, etc. may be mentioned. Further, the copolymerization of a monomer having a phenolic hydroxyl group with a styrene derivative, a (meth) acrylic acid derivative, etc. It may be a resin or the like in which two or more kinds of monomers having a phenolic hydroxyl group are copolymerized. Further, a resin obtained by modifying the above resin with an acid-labile group or a group containing an acid-labile group (hereinafter referred to as a modified resin) may be used. In order to obtain high resolution and high contrast characteristics, the modified resin is preferable. preferable. Examples of the acid labile group include those known as groups capable of being cleaved by an acid, and specifically, t-butyl, t-amyl, 1-methylcyclopentyl or 1
-Ethers, esters, or carbonates of tertiary alkyl such as methylcyclohexyl. In addition, ethers, esters or carbonates of substituted allyl groups are also useful acid labile groups.

The molecular weight of the above resin is not particularly limited, but the upper limit is preferably 10 from the viewpoint of resolution.
It is preferably 30,000, more preferably 30,000, and the lower limit is preferably 1,000, more preferably 2,000 from the viewpoint of film formability. The resin used in the present invention may be one that can be obtained by a conventional method.

Radiation-sensitive component (b) The radiation-sensitive component (b) used in the present invention is
There is no particular limitation as long as it is a substance that generates a Bronsted acid or a Lewis acid when exposed to activating radiation (hereinafter referred to as PAG), and an onium salt, a halogenated organic compound,
Use known compounds such as quinonediazide compounds, α, α-bis (sulfonyl) diazomethane compounds, α-carbonyl-α-sulfonyldiazomethane compounds, sulfone compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds You can 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.

The halogenated organic compounds include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds,
Halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, other halogen-containing heterocyclic compounds, halogen-containing aliphatic hydrocarbon compounds,
Examples thereof include halogen-containing aromatic hydrocarbon compounds and sulfenyl halide compounds. Specifically, tris (2,
3-dibromopropyl) phosphate, tris (2,3
-Dibromo-3-chloropropyl) phosphate, tetrabromochlorobutane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, allyltribromophenyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, tetrachlorobisphenol A bis (chloroethyl) ether, tetrabromobisphenol A bis (bromoethyl) ether, bisphenol A bis (2,3-dichloropropyl) ether, bisphenol A bis (2,3-dibromopropyl) ether, tetrachlorobisphenol A's screw (2,3-
Dichloropropyl) ether, bis (2,3-dibromopropyl) ether of tetrabromobisphenol A,
Tetrachlorobisphenol S, tetrabromobisphenol S, tetrachlorobisphenol S bis (chloroethyl) ether, tetrabromobisphenol S bis (bromoethyl) ether, bisphenol S bis (2,3-dichloropropyl) ether, bisphenol S bis (2,3-dibromopropyl) ether,
Tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4- (2-hydroxyethoxy) -3,5- Halogen-based flame retardants such as 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-trichloroethanol, 2,4,4 ', 5-tetrachlorodiphenyl sulfide, 2,4,4', 5-tetrachlorodiphenyl sulfone and other organic chloro-based pesticides are exemplified. It

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.

The α, α-bis (sulfonyl) diazomethane compounds include unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group,
Examples include α, α-bis (sulfonyl) diazomethane having 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-
Examples thereof include sulfonyldiazomethane. 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 thereof 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 60 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 it exceeds 60 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.

Specific Compound (c) The specific compound (c) used in the present invention is a compound containing a substituted allyloxy group having one or more substituents, and the substituted allyloxy group having one or more substituents is Any group may be used as long as it functions as an acid labile group to be decomposed. Specific examples thereof 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 one of R ^{1 to} R ⁵ is a substituent other than a hydrogen atom, R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ each independently form a ring. Each group has a carbon number of 12 or less).

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, pentyl group, cyclopentyl group,
Substitutable alkyl groups such as cyclohexyl group, cycloheptyl group, 1-methylcyclopentyl group, 2-ethylcyclopentyl group, 1-ethylcyclohexyl group, 2-methylcyclohexyl group; vinyl group, 1-propenyl group, allyl group, 1- Butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, hexenyl group, 2-cyclobutenyl group, 2-cyclopentenyl group, 1-methyl −
2-cyclopentenyl group, 2-cyclohexenyl group, 3
-Substitutable alkenyl group such as methyl-2-cyclohexenyl group; 2,4-cyclopentadienyl group, 1-methyl-2,4-cyclopentadienyl group, 3-methyl-2,
4-cyclopentadienyl group, 3,4-dimethyl-2,
Substitutable cycloalkadienyl groups such as 4-cyclopentadienyl group, 2,5-cyclohexadienyl group and 3,5-dimethyl-2,5-cyclohexadienyl group; vinyl group, 1-propenyl group, 1 -Buten-1-yl group, 1-
Examples thereof include substituted vinyl groups such as butene-2-yl group and 2-buten-2-yl group. In the specific examples of the substituent, propyl represents n-propyl and isopropyl, butyl represents n-butyl, isobutyl, s-butyl and t-butyl, pentyl represents n-pentyl, 1-methylbutyl and 2-methylbutyl. , 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl and 2,2-dimethylpropyl. Furthermore,
R ¹ and R ⁴ may combine to form a ring such as cyclohexene or cyclopentene, and similarly R 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. 1-4 alkenyl groups are preferred.

Specific examples of preferred compounds having a substituted allyloxy group of the present invention include the following formulas (2) to (18)

Embedded image

[Chemical 4]

Embedded image

[Chemical 6]

[Chemical 7]

Embedded image

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

Embedded image

[Chemical 15]

Embedded image

[Chemical 17]

Embedded image

[Chemical 19] General formula such as (19)

Embedded image (In the formula (19), R ^{1 to} R ⁵ may be the same or different from each other, and a hydrogen atom, a halogen atom, a nitro group, a cyano group,
It is a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group, a substitutable vinyl group, and at least one of R ^{1 to} R ⁵ is a substituent other than a hydrogen atom. R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ may independently form a ring. R ^{6 to} R ⁷ are a hydrogen atom or a substitutable alkyl group. R ^{8 to} R ⁹ are a halogen atom, an alkyl group,
A cyano group and a nitro group. X is a divalent organic group.
Each group has 12 or less carbon atoms. ) A compound represented by the following formulas (20) to (21)

[Chemical 21]

[Chemical formula 22] General formula such as (22)

[Chemical formula 23] (In formula (22), R ^{1 to} R ⁵ may be the same or different from each other, and a hydrogen atom, a halogen atom, a nitro group, a cyano group,
It is a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group, a substitutable vinyl group, and at least one of R ^{1 to} R ⁵ is a substituent other than a hydrogen atom. R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ may independently form a ring. R ^{6 to} R ⁸ are hydrogen atoms or alkyl groups, R ⁹ is a halogen atom, an alkyl group, a cyano group,
It is a nitro group, and X is a divalent organic group. Each group has 12 or less carbon atoms. ) A compound represented by the following formulas (23) to (24)

[Chemical formula 24]

[Chemical 25] General formula such as (25)

[Chemical formula 26] (In formula (25), R ^{1 to} R ⁵ may be the same or different from each other, and a hydrogen atom, a halogen atom, a nitro group, a cyano group,
It is a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group, a substitutable vinyl group, and at least one of R ^{1 to} R ⁵ is a substituent other than a hydrogen atom. R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ may independently form a ring. R ^{6 to} R ⁷ are hydrogen atoms or alkyl groups, R ^{8 to} R ⁹ are halogen atoms, alkyl groups, cyano groups and nitro groups, and X is a single bond or a divalent organic group. Each group has 12 or less carbon atoms. ) Compounds represented by the following formulas (26) to (29):

[Chemical 27]

[Chemical 28]

[Chemical 29]

Embedded image General formula (30) such as

[Chemical 31] (In formula (30), R ^{1 to} R ⁵ may be the same or different from each other, and a hydrogen atom, a halogen atom, a nitro group, a cyano group,
It is a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group, a substitutable vinyl group, and at least one of R ^{1 to} R ⁵ is a substituent other than a hydrogen atom. R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ may independently form a ring. R ^{6 to} R ⁷ are hydrogen atoms or alkyl groups, R ^{8 to} R ⁹ are halogen atoms, alkyl groups, cyano groups and nitro groups, and n is an integer. Each group has 12 or less carbon atoms. ) A compound represented by the following formula (31) to (33)

Embedded image

[Chemical 33]

Embedded image General formula such as (34)

Embedded image (In formula (34), R ^{1 to} R ⁵ may be the same or different from each other, and a hydrogen atom, a halogen atom, a nitro group, a cyano group,
It is a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group, a substitutable vinyl group, and at least one of R ^{1 to} R ⁵ is a substituent other than a hydrogen atom. R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ may independently form a ring. The carbon number of each of R ^{1 to} R ⁵ is 12 or less. R ⁶ is a monovalent organic group having 10 or more carbon atoms and having 2 or more rings. A compound represented by the following formula (3)
5) ~ (38)

Embedded image

Embedded image

[Chemical 38]

[Chemical Formula 39] General formula such as (39)

[Chemical 40] (In formula (39), R ^{1 to} R ⁵ may be the same or different from each other, and a hydrogen atom, a halogen atom, a nitro group, a cyano group,
It is a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group, a substitutable vinyl group, and at least one of R ^{1 to} R ⁵ is a substituent other than a hydrogen atom. R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ may independently form a ring. A is a single bond or a divalent organic group. Each group has 12 or less carbon atoms. ) A compound represented by the following formula (40) to (45)

Embedded image

Embedded image

[Chemical 43]

[Chemical 44]

Embedded image

Embedded image General formula such as (46)

[Chemical 47] (In formula (46), R ^{1 to} R ⁵ may be the same or different from each other, and a hydrogen atom, a halogen atom, a nitro group, a cyano group,
It is a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group, a substitutable vinyl group, and at least one of R ^{1 to} R ⁵ is a substituent other than a hydrogen atom. R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ may independently form a ring. X is a divalent organic group. Each group has 12 or less carbon atoms. ) A compound represented by the following formula (47) to (48)

Embedded image

[Chemical 49] General formula such as (49)

Embedded image (In formula (49), R ^{1 to} R ⁵ may be the same or different from each other, and a hydrogen atom, a halogen atom, a nitro group, a cyano group,
It is a substitutable alkyl group, a substitutable alkenyl group, a substitutable alkadienyl group, a substitutable vinyl group, and at least one of R ^{1 to} R ⁵ is a substituent other than a hydrogen atom. R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ may independently form a ring. ) Is exemplified.

The general formulas (19), (22) and (2)
5), (30), (34) and (39), R ¹ to
Specific examples of the substituent of R ⁵ include the same groups as those in the above formula (1), and among them, an alkyl group having 1 to 4 carbon atoms is preferable. R ⁶ to R ⁹ in the general formula (19), R in R ⁶ to R ⁸ in the general formula (22), and the general formula (25) to (30)
^As the substituent of ^{6 to} R ^7, a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable. General formulas (19), (22),
Specific examples of the divalent organic group represented by X in (25) and (46) include —SO ₂ —, —C (═O) —, and the following formula (50).

[Chemical 51] (In the formula (50), m is 0 or 1.) The following formula (51)

Embedded image (In the formula (51), R ^{11 to} R ¹² are a hydrogen atom, an alkyl group,
The phenyl group or R ¹¹ and R ¹² may be taken together to form a ring. Each group has 12 or less carbon atoms. ) And preferred examples of R ¹¹ and R ¹² in the formula (51) include a hydrogen atom, a methyl group, a phenyl group, and a group in which R ¹¹ and R ¹² are taken together to form a cyclohexyl ring. Specific examples of the divalent organic group represented by A in the general formula (39) include compounds represented by the above formula (51).
And the following equation (52)

Embedded image (In the formula (52), R ^{11 to} R ¹² are a hydrogen atom or a carbon number 1
It is an alkyl group of 2 or less. ) Is mentioned. When an alkyl group is selected as each of the above-mentioned substituents, a methyl group is particularly preferable because of ease of synthesis.

Among the above-mentioned compounds, particularly the compounds of formulas (12) and (1
3), (14), (15), (16), (17), (2
0), (24), (34), (37), (43), (4
4) and (48) are preferred compounds.

The compound having a substituted allyloxy group used in the present invention may be used alone or in combination of two or more kinds. The compounded amount of these compounds is usually 2 parts by weight, preferably 8 parts by weight, and 100 parts by weight, preferably 80 parts by weight, with respect to 100 parts by weight of the resin used in the present invention. If the amount is less than 2 parts by weight, it may be impossible to form a pattern.
If the amount is more than parts by weight, adverse effects such as deterioration of film formability may occur, and therefore, both are not preferable.

Solvent In the present invention, the resist composition comprising a resin binder, PAG and a specific compound having a substituted allyloxy group having one or more substituents is used by dissolving it in a solvent. As the solvent, those generally used as solvents for resist compositions can be used, and specific examples thereof include ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, cycloheptanone; n-propanol, i. -Alcohols such as propanol, n-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 Alcohol ethers such as ether and propylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate Esters such as ethyl propionate, methyl butyrate and ethyl butyrate; Oxycarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate; cellosolve Cellosolve esters such as 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; diethylene glycol Recall monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Diethylene glycols such as dimethyl ether and diethylene glycol diethyl ether; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylacetamide, Examples thereof include polar solvents such as N-methylpyrrolidone, and these may be used alone or in combination of two or more kinds.

Other Components In the present invention, compatible additives such as surfactants, storage stabilizers, sensitizers, and anti-striation agents are generally added to the resist composition as additives. Can be included.

Developer Solution In the resist composition of the present invention, an alkali aqueous solution is usually used as a developer, and specific examples thereof include an aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium silicate and ammonia; ethylamine, An aqueous solution of primary amines such as propylamine; an aqueous solution of secondary amines such as diethylamine and dipropylamine; an aqueous solution of tertiary amines such as trimethylamine and triethylamine;
Aqueous solution of alcohol amines such as diethylethanolamine and triethanolamine; fourth such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide Examples thereof include aqueous solutions of primary ammonium hydroxide. Also, if necessary, methanol, ethanol, propanol, in the above alkaline aqueous solution,
A water-soluble organic solvent such as ethylene glycol, a surfactant, and a resin dissolution inhibitor can be added.

Resist Composition The resist composition of the present invention contains the above-mentioned resin, acid generator, specific compound and, if necessary, additives, which are usually dissolved in a solvent. 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).
The sensitivity can be increased by carrying out.

The resist pattern obtained using the resist composition of the present invention can be further irradiated with actinic radiation to improve the thermal characteristics of the pattern. Examples of the actinic radiation source used include a high pressure mercury lamp, a low pressure mercury lamp, a fluorescent lamp, an incandescent lamp, and the like, and a high pressure mercury lamp and a low pressure mercury lamp are preferable. The treatment temperature at this time is not particularly limited, but is preferably 60 ° C to 130 ° C. If it is less than 60 ° C, a sufficient curing effect cannot be produced, and 1
If the temperature exceeds 30 ° C., deterioration of the pattern shape may be observed before curing, which is not preferable. It can be said that the resist pattern thus obtained is excellent not only in resist characteristics such as sensitivity and resolution but also in heat resistance.

[0027]

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 Synthesis of 2-butenyl bromoacetate 2-buten-1-ol 36.8 g (0.51 mo)
l), 51.6 g of triethylamine (0.51 mo
1) and 300 ml of dichloromethane were charged into a 1-liter flask and cooled to 0 ° C. While stirring this at 0 ° C., 100.9 g (0.50) of bromoacetyl bromide
(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, washed with water three times and then distilled to obtain 50.2 g of 2-butenyl bromoacetate.

Reference Example 2 Synthesis of 1-methyl-2-propenyl bromoacetate Reference was made except that 36.8 g (0.51 mol) of 3-buten-2-ol was used instead of 2-buten-1-ol. By the same method as in Example 1, 27.2 g of 1-methyl-2-
Propenyl bromoacetate was obtained.

Reference Example 3 3-Methyl-2-butenyl
Synthesis of bromoacetate By the same method as in Reference Example 1 except that 4-methyl-3-buten-1-ol 43.9 g (0.51 mol) was used instead of 2-buten-1-ol, 66.5 g of 3-
Methyl-2-butenyl bromoacetate was obtained.

Reference Example 4 1-Methyl-2-butenyl
Synthesis of bromoacetate 3-pentene-2-instead of 2-buten-1-ol
48.5 g of 1-methyl-2 was prepared in the same manner as in Reference Example 1, except that all 43.9 g (0.51 mol) was used.
-Butenyl bromoacetate was obtained.

(Reference Example 5) Synthesis of 1,1-dimethyl-2-propenyl bromoacetate 43.9 g (0.51 mol) of 2-methyl-3-buten-2-ol instead of 2-buten-1-ol 25.4 g of 1, by the same method as in Reference Example 1 except that
1-Dimethyl-2-propenyl bromoacetate was obtained.

Reference Example 6 Synthesis of 2-cyclohexenyl bromoacetate Reference Example 1 except that 50.0 g (0.51 mol) of 2-cyclohexen-1-ol was used instead of 2-buten-1-ol. By the same method, 50.4 g of 2-cyclohexenyl bromoacetate was obtained.

Reference Example 7 3-Methyl-2-butenyloxycarbonylmethylation Synthesis of hydrogenated polyhydroxystyrene 10% hydrogenated polyhydroxystyrene 12.0 g (M
w = 4,900) and 100 ml of DMF were placed in a 500 ml flask and dissolved. Here, 4.1 g (0.02 mo) of 3-methyl-2-butenyl bromoacetate
l), anhydrous potassium carbonate 6.9 g (0.05 mol),
8.3 g (0.05 mol) of potassium iodide was added,
It stirred at 50 degreeC under nitrogen stream for 10 hours. After that, the reaction solution was cooled, salts were removed by filtration, and the mixture was poured into water and the deposited precipitate was recovered. The precipitate was washed with 0.1% hydrochloric acid and water three times each and dried to obtain 13.7 g of polymer 3-methyl-2-butenyloxycarbonylmethylated hydrogenated polyhydroxystyrene. The obtained polymer is GPC
As a result of the analysis, Mw was 5,640. As a result of ¹ H-NMR spectrum analysis of this polymer, the modification ratio of the hydroxyl group was 15%.

Reference Example 8 4-hydroxystyrene / t
-Synthesis of butyl methacrylate copolymer 4-hydroxystyrene 72.1 g (0.60 mo
1), t-butyl methacrylate 17.1 g (0.1
2 mol), azobisisobutyronitrile 1.5 g
(0.009 mol), dioxane 150 ml 500
The mixture was placed in a ml flask and stirred under a nitrogen stream at 80 ° C. for 20 hours. The obtained reaction liquid was put into 5 liter of xylene, and the generated precipitate was filtered. The obtained precipitate was dissolved in 200 ml of diethyl ether, poured into 3 l of n-hexane, and the formed precipitate was filtered (reprecipitation operation). This reprecipitation operation was repeated 3 times, and after drying 26.
3 g of 4-hydroxystyrene / t-butyl methacrylate copolymer was obtained. As a result of GPC analysis, the obtained polymer was Mw = 6,410. Also, of this polymer
As a result of ¹ H-NMR spectrum analysis, the copolymerization ratio of 4-hydroxystyrene / t-butyl methacrylate was 7
It was 1/29.

(Synthesis Example 1) Synthesis of bisphenol-A bis (3-methyl-2-butenyl) ether 17.9 g of 1-bromo-3-methyl-2-butene (0.
12 mol) and bisphenol-A 11.4 g (0.
(05 mol) was charged into a 300 ml flask, and DMF1 was added.
After dissolving in 00 ml, anhydrous potassium carbonate 16.6 g
(0.12 mol), 19.9 g of potassium iodide (0.
12 mol) was added, and the mixture was stirred at 40 ° C. for 10 hours. Then, the reaction liquid was cooled, and salts were filtered and concentrated. The obtained crude product was dissolved in 100 ml of dichloromethane, washed with a 5% aqueous potassium hydroxide solution and a saturated saline solution three times each, dried over magnesium sulfate, and then the solvent was distilled off to obtain 14.7 g of bisphenol-A. Bis (3-methyl-2-butenyl) ether (the above formula (4
2)) was obtained.

(Synthesis Example 2) O, O'-bis (3-methyl-2-butenyl) -modified bis (4-hydroxyphenyl)
Synthesis of sulfone 15.8 g of O, O′-bis (was prepared in the same manner as in Synthesis Example 1 except that 12.5 g (0.05 mol) of bis (4-hydroxyphenyl) sulfone was used instead of bisphenol-A. 3-Methyl-2-butenyl) bis (4-hydroxyphenyl) sulfone (the above formula (4
3)) was obtained.

(Synthesis Example 3) Hydroquinone bis (3-
Methyl-2-butenyl) Synthesis of ether Hydroquinone 5.5 g instead of bisphenol-A
In the same manner as in Synthesis Example 1 except that (0.05 mol) was used, 10.0 g of hydroquinone bis (3-methyl-2-butenyl) ether (formula (47)) was obtained.

(Synthesis Example 4) Synthesis of O, O'-bis (2-butenyloxycarbonylmethyl) bisphenol A 17.4 g (0.0) of the bromoester obtained in Reference Example 1
9 mol), bisphenol-A 11.4 g (0.05
(mol) was dissolved in 100 ml of DMF, 16.6 g (0.12 mol) of anhydrous potassium carbonate and 19.9 g (0.12 mol) of potassium iodide were further added, and the mixture was stirred at 50 ° C. for 10 hours. Then, the reaction solution was cooled, salts were filtered, and concentrated. The obtained crudely purified product was dissolved in 50 ml of dichloromethane, washed with 5% potassium carbonate aqueous solution and saturated saline each three times, dried over magnesium sulfate, and then the solvent was distilled off to obtain 18.1 g of O and O ′. -Bis (2-butenyloxycarbonylmethyl) bisphenol A (formula (13)) was obtained.

(Synthesis Example 5) Synthesis of O, O'-bis (1-methyl-2-propenyloxycarbonylmethyl) bisphenol A Instead of the bromoester obtained in Reference Example 1, Reference Example 2 was used.
17.4 g (0.09mo) of the bromo ester obtained in
l) By the same method as in Synthesis Example 3 except that 18.
3 g of O, O′-bis (1-methyl-2-propenyloxycarbonylmethyl) bisphenol-A (formula (14)) was obtained.

(Synthesis Example 6) Synthesis of O, O'-bis (3-methyl-2-butenyloxycarbonylmethyl) bisphenol A Instead of the bromoester obtained in Reference Example 1, Reference Example 3 was used.
18.6 g (0.09mo) of the bromoester obtained in
l) By the same method as in Synthesis Example 3 except for using 19.
0 g of O, O'-bis (3-methyl-2-butenyloxycarbonylmethyl) bisphenol A (the above formula (1
2)) was obtained.

(Synthesis Example 7) Synthesis of O, O'-bis (1-methyl-2-butenyloxycarbonylmethyl) bisphenol-A Reference Example 4 instead of the bromoester obtained in Reference Example 1
18.6 g (0.09mo) of the bromoester obtained in
l) By the same method as in Synthesis Example 3 except that 18.
9 g of O, O′-bis (1-methyl-2-butenyloxycarbonylmethyl) bisphenol-A (the above formula (1
6)) was obtained.

(Synthesis Example 8) Synthesis of O, O'-bis (1,1-dimethyl-2-propenyloxycarbonylmethyl) bisphenol-A Instead of the bromoester obtained in Reference Example 1, Reference Example 5 was used.
18.6 g (0.09mo) of the bromoester obtained in
l) By the same method as in Synthesis Example 3 except that 18.
6 g of O, O′-bis (1,1-dimethyl-2-propenyloxycarbonylmethyl) bisphenol-A (formula (17)) was obtained.

(Synthesis Example 9) O, O'-bis (2-cyclohexenyloxycarbonylmethyl) bisphenol-
Synthesis of A Reference Example 6 instead of the bromoester obtained in Reference Example 1
19.7 g (0.09mo) of the bromoester obtained in
l) By the same method as in Synthesis Example 3 except for using 19.
7 g of O, O′-bis (2-cyclohexenyloxycarbonylmethyl) bisphenol-A (the above formula (1
5)) was obtained.

(Synthesis Example 10) Synthesis of tris (4- (3-methyl-2-butenyloxycarbonylmethyloxy) phenyl) methane 9.7 g of tris (4-hydroxyphenyl) methane in place of bisphenol-A ( 0.033 mol), but 14.7 g of tris (4- (3-methyl-2-butenyloxycarbonylmethyloxy) phenyl) methane (formula (20)) was prepared by the same method as in Synthesis Example 5.
I got

(Synthesis Example 11) Synthesis of 1,1,2,2-tetrakis (4- (3-methyl-2-butenyloxycarbonylmethyloxy) phenyl) ethane 1,2,1 instead of bisphenol-A 10.0 g of 2-tetrakis (4-hydroxyphenyl) ethane
(0.025 mol) By the same method as in Synthesis example 5 except that 14.9 g of 1,1,2,2-tetrakis (4- (3-methyl-2-butenyloxycarbonylmethyloxy) phenyl) was used. Ethane (formula (24) above) was obtained.

(Synthesis Example 12) O, O ', O''-tris (3-methyl-2-butenyloxycarbonylmethyl)
Synthesis of 2,6-bis (2-hydroxy-5-methylbenzyl) p-cresol 2,6-bis (2-hydroxy-5-methylbenzyl) p-cresol was used in place of bisphenol-A.
21.9 g of O, O ′, O ″ -tris (3-methyl-2-butenyloxycarbonylmethyl) was prepared by the same method as in Synthesis Example 5 except that 5 g (0.033 mol) was used.
Thus, 2,6-bis (2-hydroxy-5-methylbenzyl) p-cresol (formula (27)) was obtained.

(Synthesis Example 13) Synthesis of 3-methyl-2-butenyl 1-adamantane carboxylate 3-methyl-2-buten-1-ol 2.6 g (0.0
3 mol), 3.1 g of triethylamine (0.025 m)
ol) and 20 ml of THF are charged into a flask and dissolved. 1-adamantane carbonyl while stirring this
Chloride 5.0 g (0.025 mol) in THF40
What was dissolved in ml was added dropwise over 1 hour, and further 5
Stirring was continued for hours. After removing salts from the reaction solution by filtration, concentration was performed. Next, 70 ml of the crude product obtained
In ethyl acetate, washed with 5% aqueous sodium hydrogen carbonate solution and saturated saline three times each, dried over magnesium sulfate and evaporated to remove 4.9 g of 3-.
Methyl-2-butenyl 1-adamantane carboxylate (formula (33)) was obtained.

Synthesis Example 14 Synthesis of O, O'-bis (3-methyl-2-butenyloxycarbonylmethyl) hydroquinone Hydroquinone 5.5 g instead of bisphenol A
By the same method as in Synthesis Example 5 except that (0.05 mol) was used, 15.9 g of O, O′-bis (3-methyl-
2-Butenyloxycarbonylmethyl) hydroquinone (formula (37)) was obtained.

(Examples 1 to 14) 15% 3-methyl-2-butenyloxycarbonylmethyl hydrogenated polyhydroxystyrene obtained by the method of Reference Example 7 (Mw =
5, 640) 100 parts, 40 parts of each of the specific compounds obtained in Synthesis Examples 1 to 14, 5 parts of triphenylsulfonium triflate as a photoacid generator, 0.01 part of a fluorochemical surfactant and ethyl lactate 460. Dissolved in 0.1 part, 0.1μ
Then, the solution was filtered through a polytetrafluoroethylene filter (Millipore) to prepare a resist solution. These resist solutions were 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. These wafers were exposed using an excimer stepper (NA = 0.45) and a test reticle. Then, the wafers coated with the resist solution containing the specific compound of Synthesis Examples 4 and 5 are baked at 110 ° C. for 60 seconds, and Synthesis Example 1 to
The wafer coated with the resist solution containing 3, 6 to 14 of the specific compound was baked at 90 ° C. for 60 seconds. Then, the dipping phenomenon was performed on each wafer with an aqueous solution of tetramethylammonium hydroxide to obtain a positive pattern. The sensitivity and resolution of the obtained resist film were as shown in Table 1.

[0051]

[Table 1]

Example 15 The copolymer of 4-hydroxystyrene / t-butylmethacrylate obtained in Reference Example 8 (copolymerization ratio 71:29, Mw = 6,410) was used as 10 parts.
0 part, 40 parts of the specific compound obtained in Synthesis Example 6, triphenylsulfonium triflate 5 as a photo-acid generator
Part, and 0.01 part of a fluorine-based surfactant activator were dissolved in 460 parts of ethyl lactate and filtered through a 0.1 μm polytetrafluoroethylene filter (manufactured by Millipore) to prepare a resist solution. This resist solution 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 was excimer stepper (NA = 0.
45) and a test reticle were used for exposure. Then, baking was performed at 90 ° C. for 60 seconds, and then, a dipping phenomenon was performed with an aqueous solution of tetramethylammonium hydroxide to obtain a positive pattern.

(Example 16) Novolac resin (m-cresol / p-cresol = 5/5, Mw = 4,850)
100 parts, 50 parts of the specific compound obtained in Synthesis Example 6, 5 parts of triphenylsulfonium triflate as a photoacid generator, and 0.01 parts of a fluorosurfactant were dissolved in 460 parts of ethyl lactate to give 0. A resist solution was prepared by filtering with a 1 μm polytetrafluoroethylene filter (manufactured by Millipore). This resist solution was spin-coated on a silicon wafer and then baked at 105 ° C. for 90 seconds to form a resist film having a thickness of 1.0 μm. Electron beam drawing was performed on this wafer using an electron beam drawing apparatus (accelerating voltage: 30 keV). Then, baking was performed at 90 ° C. for 60 seconds, and then, a dipping phenomenon was performed with an aqueous solution of tetramethylammonium hydroxide to obtain a positive pattern. The sensitivity and resolution of the resist films obtained in Examples 15 and 16 are as shown in Table 2.

[0054]

[Table 2]

Example 17 Using the resist composition used in Example 15, a 5 μm line & space resist pattern was obtained in the same manner as in Example 15. The resist pattern was subjected to UV cure treatment (90 ° C./high-pressure mercury lamp irradiation for 1.5 minutes), and a heat resistance test was performed with an untreated resist pattern. As a result, in the untreated pattern, the deterioration of the shape was recognized at 110 ° C. or higher, but in the processed pattern, the deterioration of the shape was not recognized even at 160 ° C. The results are shown in Table 3.

[0056]

[Table 3]

As described above, it was found that the composition of the present invention can provide very excellent properties as a resist.

[0058]

As described above, according to the present invention, a resist composition having excellent resist properties such as sensitivity and resolution can be obtained.
In addition, since the pattern obtained using the resist can be improved in heat resistance by irradiation with actinic radiation, it is possible to obtain a finely processed semiconductor element with high accuracy.

Claims (2)

[Claims] 1. A radiation-sensitive composition comprising a resin binder (a), a radiation-sensitive component (b) that produces an acid when exposed to activating radiation, and a specific compound (c). A resist composition wherein (c) is a compound containing a substituted allyloxy group having one or more substituents. 2. The substituted allyloxy group of the specifier compound (c) 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 one of R ^{1 to} R ⁵ is a substituent other than a hydrogen atom, R ¹ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁵ each independently form a ring. Each of the groups has a carbon number of 12 or less.) The resist composition according to claim 1, wherein