JPH08179500A - Chemical amplification type resist solution - Google Patents

Abstract

PURPOSE: To obtain a novel resist soln. excellent in shelf stability and giving a resist film excellent in sensitivity to radiation and resolution by incorporating a specified compd. as a component of a solvent. CONSTITUTION: This resist soln. contains propylene glycol alkyl ether propionate as a component of the solvent and gives a resist film excellent in sensitivity and resolution, practically free from unevenness in coating and cloudiness, having a smooth surface, capable of stable fine working, excellent in shelf stability and giving a satisfactory pattern shape. The resist film is adaptable to UV such as i-line, far UV such as KrF excimer laser light, X-rays such as synchrotron radiation, charged corpuscular beams such as electron beams or any other radiation. This resist soln. is useful as a soln. for forming a chemical amplification type resist film for producing IC.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a chemically amplified resist solution. More specifically, ultraviolet rays, far ultraviolet rays, X-rays,
The present invention relates to a chemically amplified resist solution that can be suitably used when performing ultrafine processing of a semiconductor using radiation such as a charged particle beam.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuits, a technique for further miniaturizing a processing size in lithography has been developed and put into practical use in order to obtain a higher degree of integration of integrated circuits. There is. In recent years, 0.
There is a need for a technique capable of stably performing fine processing of 5 μm or less. Therefore, even in the resist used, it is necessary to accurately form a pattern of 0.5 μm or less, and various resists have been studied. Of these, the resist that attracts particular attention is a resist that causes a reaction that changes the solubility of a radiation-irradiated portion in a developing solution by the catalytic action of an acid generated by irradiation of radiation. This type of resist is usually called a chemically amplified resist. When actually using this chemically amplified resist in the integrated circuit manufacturing process,
Prepare a resist solution in which the radiation-sensitive components constituting the resist such as the radiation-sensitive components and film-forming resin components are dissolved in a solvent, and apply this solution by spin coating or roll coater on the substrate to be subjected to microfabrication. Then, a resist film is formed. Therefore, performances such as coating property and storage stability of the resist solution are indispensable performances for stably performing advanced fine processing. By irradiating the resist coating with radiation, a pattern suitable for fine processing is formed from the resist coating. The shape of the formed pattern has an important influence on the precision of fine processing, and a pattern having a rectangular cross section is preferable.

Further, in a resist using a novolak resin and a sensitizer containing a naphthoquinonediazide group, which has been conventionally used for lithography, ethylene glycol monoethyl ether acetate is used as a solvent for preparing a resist solution. It is known. However, for chemically amplified resists, there is a problem in storage stability when ethylene glycol monoethyl ether acetate is used as a solvent when preparing a resist solution. That is, when ethylene glycol monoethyl ether acetate is used as a solvent, there is a problem that the sensitivity of the resist film and the shape of the formed pattern vary with the passage of time after preparation of the resist solution. Furthermore, with the recent increase in the degree of integration of integrated circuits, the diameter of silicon wafers has been increased, for example, from 4 inches to 6 inches or 8 inches in order to improve the yield and efficiency at the time of manufacturing integrated circuits. . As a solvent for chemically amplified resist, when a chemically amplified resist solution using conventionally general ethylene glycol monoethyl ether acetate is applied to a substrate with a large diameter by spin coating, the resulting resist film is There is a problem to be improved from the viewpoint of coating properties such as radial or spotted coating unevenness, clouding, and insufficient surface smoothness of the coating.

[0004]

The object of the present invention is to provide ultraviolet rays represented by i-rays (365 nm), deep ultraviolet rays represented by KrF excimer lasers (248 nm), X-rays represented by synchrotron radiation, and electrons. It is to provide a novel chemically amplified resist solution that provides a resist film having excellent sensitivity and resolution to a radiation such as a charged particle beam represented by a beam. Another object of the present invention is to provide a resist film formed by spin coating on a silicon wafer substrate having a large diameter with substantially no coating unevenness and cloudiness and to have good surface smoothness. It is to provide such a chemically amplified resist solution. Another object of the present invention is to provide a chemically amplified resist solution capable of stably performing fine processing and forming a resist film capable of giving a good pattern shape having a rectangular cross section. . Still another object of the present invention is to provide a chemical composition capable of forming a resist film having good sensitivity and capable of giving an excellent pattern shape with good reproducibility even after a long time has passed after preparing a resist solution. The purpose of the present invention is to provide an amplified resist solution, that is, a chemically amplified resist solution having excellent storage stability.

[0005]

According to the present invention, there is provided a chemically amplified resist solution which is a solution of a solvent containing propylene glycol alkyl ether propionate as a component of the solvent. The above object of the invention is achieved. Hereinafter, the present invention will be described in detail, with which other objects, configurations, advantages and effects of the present invention will be apparent.

In the present invention, the chemically amplified resist means that an acid is generated in a radiation irradiation portion of the resist film by irradiating the resist film on the substrate with radiation, and a chemical change caused by a catalytic action of the generated acid is generated. A resist capable of forming a resist pattern on a substrate by utilizing the fact that the radiation-exposed portion of the resist film changes its solubility in a developing solution. Examples of the chemically amplified resist solution of the present invention include the following type A to type C resist solutions.

Type A resist solution A positive resist solution containing the following components (a) to (c). (A) Acid-decomposable group-containing resin This acid-decomposable group-containing resin is insoluble or sparingly soluble in an alkali developing solution because it contains an acid-decomposable group in the polymer chain, and is in contact with an acid to form a film. It is a resin that is hydrolyzed by the water present in the above to generate an alkali-soluble group and thereby becomes alkali-soluble. (B) Radiation-sensitive acid generator This component is a component that generates an acid upon irradiation with radiation. (C) Solvent containing propylene glycol alkyl ether propionate

Type B resist solution This is a positive resist solution containing the following components (a) to (d). (A) Alkali-soluble resin (b) Radiation-sensitive acid generator (c) Dissolution control agent This dissolution control agent controls the solubility of the above-mentioned (a) alkali-soluble resin in an alkali developer before contact with an acid. Which is a compound which is hydrolyzed by water present in the film upon contact with an acid, resulting in (i) the alkali of the above-mentioned (a) alkali-soluble resin contained in the dissolution control agent before hydrolysis. A compound that reduces or eliminates the effect of controlling the solubility in a developing solution, or (ii) rather accelerates the solubility of the alkali-soluble resin (a) in an alkaline developing solution. The use of this dissolution control agent can control the alkali solubility of the alkali-soluble resin. (D) Solvent containing propylene glycol alkyl ether propionate

Type C Resist Solution A negative resist solution containing the following components (a) to (d). (A) Alkali-soluble resin (b) Radiation-sensitive acid generator (c) Crosslinking agent This component is a compound that reacts with the above-mentioned (a) alkali-soluble resin in the presence of an acid to crosslink the resin. is there. (D) Solvent containing propylene glycol alkyl ether propionate

The constituent components of these resist solutions will be described below. Radiation-sensitive acid generator As the radiation-sensitive acid generator used in any type of the resist solution of the present invention, that is, a compound that generates an acid in response to radiation, for example, an onium salt compound, a halogen-containing compound, a sulfone is used. Examples thereof include compounds, sulfonic acid ester compounds, quinonediazide compounds and the like. More specifically, the following compounds can be mentioned.

Onium salt compounds Examples of onium salts include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts and pyridinium salts. Preferred onium salt compounds are diphenyliodonium triflate, diphenyliodonium pyrene sulfonate,
Diphenyliodonium dodecylbenzene sulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate and (hydroxyphenyl) benzylmethylsulfonium toluene sulfonate, especially triphenylsulfonium triflate Rate and diphenyliodonium hexafluoroantimonate are preferred.

Halogen-Containing Compound Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferred halogen-containing compounds are phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl)-.
s-triazine, naphthyl-bis (trichloromethyl)
(Poly) trichloromethyl such as -s-triazine-s-
Triazine derivatives and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.

Sulfone compound Examples of the sulfone compound include β-ketosulfone and β-ketosulfone.
-Sulfonyl sulfone, these α-diazo compounds and the like can be mentioned. Preferred sulfone compounds are phenacylphenyl sulfone, mesitylphenacyl sulfone, bis (phenylsulfonyl) methane, bis (phenylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane and 4-trisphenacylsulfone.

Sulfonic Acid Ester Compound Examples of the sulfonic acid ester compound include alkyl sulfonic acid ester, haloalkyl sulfonic acid ester,
Aryl sulfonate, imino sulfonate, etc. can be mentioned. Preferred sulfonic acid ester compounds are benzoin tosylate, pyrogallol tris triflate, pyrogallol methane sulfonic acid triester, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, N-trifluoromethylsulfonyloxydiphenylmaleimide and trifluoro. Methylsulfonyloxybicyclo- [2.2.1] -hept-
5-ene-2,3-dicarboximide and the like, and pyrogallol methanesulfonic acid triester is particularly preferable.

Quinonediazide Compound Examples of the quinonediazide compound include 1,2-quinonediazide sulfonic acid ester compounds of polyhydroxy compounds. Preferred quinonediazide compounds are 1,2-benzoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-5-sulfonyl group and 1,2-naphthoquinonediazide-6-. A compound having a sulfonyl group 1,2-quinonediazidesulfonyl group, particularly a 1,2-naphthoquinonediazide-4-sulfonyl group and / or a 1,2-naphthoquinonediazide-
A compound having a 5-sulfonyl group is preferable.

Specific examples of such quinonediazide compounds include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and 2,2,6-trihydroxybenzophenone.
3,4,4'-tetrahydroxybenzophenone, 2,
2 ', 3,4-tetrahydroxybenzophenone, 3'
-Methoxy-2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, 2,2 ' , 3,4,6'-pentahydroxybenzophenone, 2,3,3 ', 4,4',
5'-hexahydroxybenzophenone, 2,3 ',
1,2-quinonediazide sulfonic acid esters of (poly) hydroxyphenyl aryl ketones exemplified by 4,4 ′, 5 ′, 6-hexahydroxybenzophenone and the like;
Bis (4-hydroxyphenyl) methane, bis (2,4
-Dihydroxyphenyl) methane, bis (2,3,4-)
Trihydroxyphenyl) methane, 2,2-bis (4-
Hydroxyphenyl) propane, 2,2-bis (2,4
-Dihydroxyphenyl) propane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, etc. 1,2-quinonediazide sulfonic acid esters of bis [(poly) hydroxyphenyl] alkanes;

4,4'-dihydroxytriphenylmethane, 4,4 ', 4 "-trihydroxytriphenylmethane, 2,2', 5,5'-tetramethyl-2", 4
4'-trihydroxytriphenylmethane, 3,3 ',
5,5'-tetramethyl-2 ", 4,4'-trihydroxytriphenylmethane, 4,4 ', 5,5'-tetramethyl-2,2', 2" -trihydroxytriphenylmethane, 2 , 2 ', 5,5'-tetramethyl-4,
4 ', 4 "-trihydroxytriphenylmethane, 1,
1,1-tris (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl)-
1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) propane, 1,1,3 1,2-quinonediazidesulfonic acid of (poly) hydroxytriphenylalkane exemplified by -tris (2,5-dimethyl-4-hydroxyphenyl) butane and 1,3,3-tris (4-hydroxyphenyl) butane Esters; 2,4,4-trimethyl-
2 ', 4', 7-trihydroxy-2-phenylflavan, 2,4,4-trimethyl-2 ', 4', 5 ', 6
1,2- of (poly) hydroxyphenyl flavans exemplified by 7-pentahydroxy-2-phenyl flavan and the like.
Examples thereof include quinonediazide sulfonic acid esters.

A particularly preferred quinonediazide compound is represented by the following structural formula (1): 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl } Phenyl] ethane 1,2-naphthoquinonediazide-4-sulfonic acid ester.

[0019]

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[Wherein each of the three Z's is independently a hydrogen atom or a group represented by the formula (2)]

[0021]

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A substituent represented by: at least 1
One is a substituent represented by the formula (2). ] In the mixture of 1,2-naphthoquinonediazide-4-sulfonic acid ester represented by the structural formula (1), the ratio of Z being the substituent represented by the formula (2) is 75 to 9 on average.
5%, preferably 80 to 90% on average.

Particularly preferred radiation-sensitive acid generators include the compounds of the following formulas (3) to (8).

[0024]

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These radiation-sensitive acid generators can be used alone or in admixture of two or more.

The acid-decomposable group-containing resin in the resist solution of the acid-decomposable group-containing resin type A is, for example, one hydrogen atom of an acidic functional group exemplified by a phenolic hydroxyl group and a carboxyl group in an alkali-soluble resin described later. Alternatively, it is a resin that is insoluble or hardly soluble in an alkali developing solution, which can be obtained by substituting two or more kinds of acid-decomposable groups. Here, the resin which is insoluble or hardly soluble in an alkali developing solution means that a resist coating formed by using a type A resist solution is irradiated with radiation and then developed by an alkali developing solution used for forming a resist pattern. Under conditions, when a coating formed from a solution containing only an acid-decomposable group-containing resin instead of the type A resist solution is developed, the film thickness before development is 50%.
% Or more is the resin remaining after development. The acid-decomposable group is
It is a group that is hydrolyzed by water in the film in the presence of an acid, and as a result, a functional group showing alkali solubility is formed to make the resin alkali soluble. Examples of such a group include a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group,
An acyl group and a cyclic acid-decomposable group can be mentioned.

Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group,
Ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, methoxyphenacyl group,
(Methylthio) phenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group, ethylthiobenzyl group and piperonyl group Can be mentioned. Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,
1-dimethoxyethyl group, 1-ethoxyethyl group, 1-
Ethylthioethyl group, 1,1-diethoxyethyl group, 1
-Phenoxyethyl group, 1-phenylthioethyl group,
1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, α-methylphenacyl group, etc. Can be mentioned.

Examples of the 1-branched alkyl group include isopropyl group, sec-butyl group, t-butyl group,
Mention may be made of a 1,1-dimethylpropyl group, a 1-methylbutyl group and a 1,1-dimethylbutyl group. Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, diethylmethylsilyl group, triethylsilyl group, dimethylisopropylsilyl group, methyldiisopropylsilyl group, triisopropylsilyl group, t
-Butyldimethylsilyl group, di-t-butylmethylsilyl group, tri-t-butylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group and triphenylsilyl group can be mentioned. Examples of the germyl group include trimethylgermyl group, ethyldimethylgermyl group, diethylmethylgermyl group, triethylgermyl group, dimethylisopropylgermyl group, methyldiisopropylgermyl group, triisopropylgermyl group, t
-Butyldimethylgermyl group, di-t-butylmethylgermyl group, tri-t-butylgermyl group, dimethylphenylgermyl group, methyldiphenylgermyl group and triphenylgermyl group can be mentioned.

Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group and t-pentyloxycarbonyl group. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauriloyl group, a myristoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group, and a succinyl group. Group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group,
Mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group and isonicotinoyl group. You can Examples of the cyclic acid-decomposable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group,
Cyclohexenyl group, oxocyclohexenyl group, 4-
Methoxycyclohexyl group, tetrahydropyranyl group,
Tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, S, S
-Dioxide group, 2-1,3-dioxolanyl group, 2-
Examples thereof include a 1,3-dithiolanyl group, a benzo-2-1,3-dioxolanyl group and a benzo2-1,3-dithiolanyl group. Other acid-decomposable groups include a toluenesulfonyl group and a mesyl group. Of these acid-decomposable groups, t-butyl group, benzyl group,
t-butoxycarbonyl group, tetrahydropyranyl group,
Tetrahydrofuranyl group, tetrahydrothiopyranyl group and tetrahydrothiofuranyl group are preferred.

The ratio of the number of acid-decomposable groups to the total number of acidic functional groups and acid-decomposable groups in the acid-decomposable group-containing resin is preferably 15 to 100%, more preferably 20 to 10%.
0%, particularly preferably 20 to 80%. The polystyrene-equivalent weight average molecular weight (hereinafter, abbreviated as "Mw") of the acid-decomposable group-containing resin measured by gel permeation chromatography is preferably 1,000 to 150,000, and more preferably 3,0
00 to 100,000. The acid-decomposable group-containing resin is
For example, by introducing one or more acid-decomposable groups into one or more preliminarily prepared alkali-soluble resins,
It can be produced by polymerizing or copolymerizing a monomer having at least one acid-decomposable group. These acid-decomposable group-containing resins can be used alone or in combination of two or more.

The mixing ratio of the acid-decomposable group-containing resin and the radiation-sensitive acid generator in the type A resist solution is preferably 0 for the radiation-sensitive acid generator per 100 parts by weight of the acid-decomposable group-containing resin. 0.05 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, and particularly preferably 0.5 to 15 parts by weight. Particularly in the resist solution of type A, the onium salt or sulfonic acid ester is preferable as the radiation-sensitive acid generator, and 0.05 to 20 parts by weight, particularly 0.5 to 12 parts by weight is preferable. When the compounding amount of the radiation-sensitive acid generator is within the above range, it is possible to more effectively cause the chemical change due to the catalytic action of the acid generated by the irradiation of radiation, and the resist solution of type A is applied. It is possible to more effectively suppress the occurrence of coating unevenness in the resulting coating and the occurrence of scum during development.

Alkali-Soluble Resin The alkali-soluble resin used in the type B and type C resist solutions is a resin soluble in an alkali developing solution. This resin has a functional group having an affinity with an alkaline developer, for example, an acidic functional group such as a phenolic hydroxyl group and a carboxyl group. Examples of such an alkali-soluble resin include hydroxystyrene, hydroxy-α-methylstyrene, vinylbenzoic acid, carboxymethylstyrene, carboxymethoxystyrene, (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, Resin produced by addition polymerization obtained by polymerizing or copolymerizing at least one monomer having an acidic functional group exemplified by mesaconic acid and cinnamic acid, and produced by condensation polymerization represented by novolac resin Other examples include resins.

When the alkali-soluble resin is a resin produced by addition polymerization, the resin may be composed of only repeating units in which the polymerizable multiple bond present in the monomer having the acidic functional group is cleaved. However, as long as it is soluble in an alkali developing solution, it may further contain other repeating units, if necessary. Examples of the monomer that gives such another repeating unit include styrene, α-methylstyrene, methoxystyrene, t-butoxystyrene, acetoxystyrene, vinyltoluene, maleic anhydride, (meth) acrylonitrile, crotonnitrile,
Malein nitrile, fumaro nitrile, mesacone nitrile, citracon nitrile, itacone nitrile, (meth)
Mention may be made of acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citracone amide, itaconamide, vinylaniline, vinylpyridine, vinyl-ε-caprolactam, vinylpyrrolidone and vinylimidazole.

When the alkali-soluble resin is a resin produced by condensation polymerization, the resin may be composed of, for example, only novolac resin units, but the produced resin is soluble in an alkali developing solution. As long as it is possible, it may further have a unit formed by other condensation polymerization. Such a resin comprises one or more phenols and one or more aldehydes, optionally together with other condensation polymerization components, in the presence of an acidic catalyst, in an aqueous medium or a mixed medium of water and a hydrophilic solvent. It can be produced by carrying out condensation polymerization or co-condensation polymerization. Examples of the phenols include o-cresol, m-cresol, p-
Cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol,
3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol and the like can be mentioned. Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde and phenylacetaldehyde.

The content of the repeating unit having an acidic functional group in the alkali-soluble resin cannot be unconditionally specified depending on the type of other repeating units contained as necessary,
Usually 15 to 100 mol%, more preferably 20 to 1
It is 00 mol%. The Mw of the alkali-soluble resin varies depending on the desired characteristics of the type B or type C resist solution, but is preferably 1,000 to 150,000, more preferably 3,000 to 100,000. When the alkali-soluble resin has a repeating unit containing a carbon-carbon unsaturated bond, it can be hydrogenated and used. In the type B or type C resist solution,
The alkali-soluble resins can be used alone or in admixture of two or more.

Dissolution Control Agent The dissolution control agent used in the type B resist solution is a compound which controls the solubility of the above-mentioned (a) alkali-soluble resin in an alkali developing solution before contact with an acid, and Upon contact, the water present in the film hydrolyzes itself, and as a result, (i) controls the solubility of the above-mentioned (a) alkali-soluble resin in the alkali developing solution which the dissolution control agent has before hydrolysis. A compound which reduces or eliminates the effect, or (ii) rather accelerates the solubility of the above-mentioned (a) alkali-soluble resin in an alkali developing solution. Examples of such a dissolution control agent include a compound in which a hydrogen atom of an acidic functional group exemplified by a phenolic hydroxyl group and a carboxyl group is replaced by an acid-decomposable group contained in the acid-decomposable group-containing resin described above. You can The acid-decomposable group-containing resin described above can be used as a dissolution control agent in a type B resist solution.

The dissolution control agent can be a low molecular weight compound or a polymer compound substituted with the above-mentioned acid-decomposable group. Preferred dissolution control agents include bisphenol A,
Examples thereof include a polyhydric phenolic compound exemplified by bisphenol F and bisphenol S, or a compound obtained by introducing the acid decomposable group into a carboxylic acid compound exemplified by hydroxyphenylacetic acid. Specific examples include compounds represented by the following chemical formulas (9) and (10).

[0038]

[Chemical 4]

In the type B resist solution, the dissolution control agent may be used alone or in combination of two or more kinds, and a low molecular compound and a high molecular compound may be used in combination. The mixing ratio of the alkali-soluble resin, the radiation-sensitive acid generator and the dissolution control agent in the type B resist solution is preferably 0.05 to 20 parts by weight per 100 parts by weight of the alkali-soluble resin. ,
It is more preferably 0.1 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight, and the dissolution control agent is preferably 5 to 150 parts by weight, more preferably 5 to 100 parts by weight, particularly preferably 5 parts by weight. ˜50 parts by weight. Particularly in the type B resist solution, the radiation-sensitive acid generator is preferably an onium salt, and at that time, 0.05 to 20 parts by weight, particularly 0.
5 to 10 parts by weight is preferable. When the weight ratio of each component satisfies the above range, it is possible to more effectively cause a chemical change due to the acid generated by the irradiation of radiation,
The uneven coating is further suppressed when the type B resist solution is applied, and scum is less likely to occur during development. In addition, the desired action based on the dissolution control agent can be more effectively obtained, and the film-forming property and film strength of the type B resist solution can be at a more appropriate level. The dissolution control agent may be added to the type A resist solution, and the addition amount in this case is preferably 50 parts by weight or less with respect to 100 parts by weight of the acid-decomposable group-containing resin.

Crosslinking Agent Next, the crosslinking agent used in the resist solution of type C is a compound capable of crosslinking the alkali-soluble resin in the presence of an acid, for example, in the presence of an acid generated by irradiation with radiation. . As such a cross-linking agent, a compound having at least one group capable of reacting with an alkali-soluble resin in the presence of an acid to form a cross-link (hereinafter, referred to as “cross-linkable group”) in the molecule. Can be mentioned. Examples of the crosslinkable group include the following formulas (11) to (15)

[0041]

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(Here, 1 is 1 or 2, and when 1 is 1, X is any one selected from a single bond, -O-, -S-, -CO-O- and -NH-. , L is 2,
X is trivalent N, Y is -O- or -S-, and m
Is an integer of 0 to 3, n is an integer of 1 to 3, and n + m is 4 or less. )

[0043]

[Chemical 6]

(Here, k is 0 or an integer of 1 or more, Z is any one selected from --O--, --CO--O-- or --CO--, and R ¹ and R ² are the same as each other. They may be different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ represents an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 14 carbon atoms.)

[0045]

[Chemical 7]

(Here, R ⁴ , R ⁵ and R ^{6, which} may be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[0047]

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(Here, k is an integer of 0 or 1 or more, R ¹
And R ² may be the same or different from each other, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ have 1 carbon atoms.
5 represents an alkoxy group or an alkoxyalkyl group. )

[0049]

[Chemical 9]

(Where k is an integer of 0 or 1 or more, R ¹
Or R ² may be the same or different from each other, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁹ has any heteroatom selected from oxygen, sulfur and nitrogen, and R ⁹ is a bond. Is a divalent organic group capable of forming a 3- to 8-membered ring including a nitrogen atom. ) And the like.

Specific examples of such a crosslinkable group include a glycidyl ether group, a glycidyl ester group, a glycidylamino group, a methoxymethyl group, an ethoxymethyl group, a benzyloxymethyl group, a dimethylaminomethyl group, a diethylaminomethyl group, a diamino group. Examples thereof include a methylolaminomethyl group, a diethylolaminomethyl group, a morpholinomethyl group, an acetoxymethyl group, a benzoyloxymethyl group, a formyl group, an acetyl group, a vinyl group and an isopropenyl group. Specific examples of the compound having a crosslinkable group, that is, a crosslinking agent, include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resole resin epoxy compounds, and poly (hydroxy). (Styrene) epoxy compound, methylol group-containing melamine compound, methylol group-containing benzoguanamine compound,
Methylol group-containing urea compound, methylol group-containing phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group-containing phenol compound, carboxymethyl group-containing melamine compound, carboxymethyl group Examples thereof include a benzoguanamine compound, a carboxymethyl group-containing urea compound, and a carboxymethyl group-containing phenol compound.

Of these crosslinking agents, a methylol group-containing phenol compound, a methoxymethyl group-containing melamine compound, a methoxymethyl group-containing phenol compound, an acetoxymethyl group-containing phenol compound, and the like are preferable, and a methoxymethyl group-containing melamine compound is more preferable. Is. Commercially available melamine compounds containing methoxymethyl group include CYMEL300, CYMEL301, and CYMEL.
303, CYMEL 305 (trade name, manufactured by Mitsui Cyanamid) and the like, and specific examples thereof include a compound (c) represented by the following formula (16).

[0053]

[Chemical 10]

As a cross-linking agent other than the above, the cross-linkable group is introduced into the acidic functional group in the alkali-soluble resin,
Resins having properties as a crosslinking agent are also suitable. In that case, the introduction rate of the crosslinkable group is usually 5 to 60 mol%, preferably 10 to 50 mol%, and more preferably 15 to 40 mol% with respect to the total amount of the acidic functional groups in the alkali-soluble resin. Adjusted. In the type C resist solution,
These cross-linking agents can be used alone or in admixture of two or more. The mixing ratio of the alkali-soluble resin, the radiation-sensitive acid generator and the crosslinking agent in the type C resist solution is preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble resin. The amount is more preferably 0.1 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight, and the crosslinking agent is preferably 5 to
95 parts by weight, more preferably 15 to 85 parts by weight, particularly preferably 20 to 75 parts by weight. Further, as the radiation-sensitive acid generator in the type C resist solution, a halogen-containing compound is preferable, and in this case, 0.05-20
Weight part, especially 0.5-10 weight part is preferable. By satisfying the above ratio, it becomes possible to more effectively cause a chemical change due to the acid catalyst generated by irradiation of radiation, and the occurrence of coating unevenness occurring in the coating film formed by coating the resist solution and scum during development. The number of occurrences of the above is further reduced, the crosslinking is more appropriately progressed, the occurrence of problems such as reduction of the residual film rate, meandering of the pattern, and swelling of the pattern is less, and the developability is more appropriate.

Various Additives Various additives such as surfactants and sensitizers may be added to the chemically amplified resist solution of the present invention, if necessary. The surfactant exhibits an action of improving the coatability and striation of the chemically amplified resist solution, the developability of the resist, and the like. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate. In addition to the rate, the product name is KP341 (produced by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95
(Manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
F303, EF352 (manufactured by Tochem Products), Megafax F171, F172, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431
(Made by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC
-103, SC-104, SC-105 and SC-10
6 (manufactured by Asahi Glass) and the like. These surfactants may be used alone or in admixture of two or more. The amount of the surfactant blended is usually 2 parts by weight calculated as the active ingredient of the surfactant per 100 parts by weight of all the resin components such as the acid-decomposable group-containing resin and the alkali-soluble resin in the chemically amplified resist solution. It is the following.

The sensitizer absorbs the energy of radiation and transfers the energy to the radiation-sensitive acid generator,
This has the effect of increasing the amount of acid produced, and has the effect of improving the apparent sensitivity of the resist film formed from the chemically amplified resist solution of the present invention. Preferred sensitizers include ketones, benzenes, acetophenones, benzophenones, naphthalenes, biacetyls, eosin, rose bengal, pyrenes, anthracenes and phenothiazines. These sensitizers may be used alone or in admixture of two or more. The compounding amount of the sensitizer is usually 50 parts by weight or less based on 100 parts by weight of all resin components such as acid-decomposable group-containing resin and alkali-soluble resin in the chemically amplified resist solution.
It is preferably 30 parts by weight or less.

By adding a dye or a pigment to the chemically amplified resist solution of the present invention, the latent image in the exposed area can be visualized to mitigate the effect of halation during exposure, and an adhesion aid is added. As a result, the adhesiveness with the substrate can be improved. Furthermore, as other additives, antihalation agents, storage stabilizers, defoaming agents and the like can be mentioned. 4-hydroxy-4'-methyl chalcone can be mentioned as a specific example of the antihalation agent.
Further, by using the nitrogen-containing compound described in JP-A-5-232706 as the shape improving agent, the resist solution of the present invention can be treated with post-time exposure time delay (PED: leaving time after exposure). The deterioration effect of the dependent pattern shape) can be further improved. As such a shape improving agent,
For example, 4,4'-diaminodiphenyl ether, nicotinic acid amide, etc. can be mentioned. In this case, the amount of the shape-improving agent used is 100% of all resin components such as acid-decomposable group-containing resin and alkali-soluble resin in the chemically amplified resist solution.
Generally, 0.001 to 10 parts by weight is preferable, and 0.01 to 5 parts by weight is particularly preferable.

Solvent The solvent used in the chemically amplified resist solution of the present invention is
A solvent containing propylene glycol alkyl ether propionate. Specific examples of the propylene glycol alkyl ether propionate include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, and propylene glycol monobutyl ether propionate. By using this solvent, the chemically amplified resist solution of the present invention has excellent storage stability. That is, for example, even after a long time has passed after preparing the resist solutions of types A to C, the resist coating formed from these resist solutions should maintain good sensitivity and give the resist pattern shape with good reproducibility. You can

The chemically amplified resist solution of the present invention may contain a solvent other than propylene glycol alkyl ether propionate as a solvent. However, it is preferable that propylene glycol alkyl ether propionate accounts for 30% by weight or more, particularly 50% by weight or more, and particularly 70% by weight or more in the solvent. Most preferred is when the solvent consists essentially of propylene glycol alkyl ether propionate. Other solvents that can be contained in the chemically amplified resist solution of the present invention include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate and other ethylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl D Diethylene dialkyl ethers such as ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol Propylene glycol dialkyl ethers such as dibutyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate; methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, Isobutyl formate, n-amyl formate, isoamyl formate, methyl acetate, ethyl acetate, n-acetate
-Propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n acetate
-Hexyl, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, Aliphatic carboxylic acid esters such as isobutyl butyrate;

Ethyl hydroxyacetate, 2-hydroxy-
Ethyl 2-methylpropionate, 2-hydroxy-3-
Methyl methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutylacetate, 3-methyl- 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate,
Other esters such as ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N -Methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N
Examples include amides such as -dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-butyrolactone.

These solvents may be used alone or in admixture of two or more. The amount of all the solvents is usually 20 to 3,000 parts by weight, preferably 100 parts by weight of all the resin components such as acid-decomposable group-containing resin and alkali-soluble resin contained in the chemically amplified resist solution. Is 50 to 3000 parts by weight, more preferably 100 to 2
000 parts by weight. The chemically amplified resist solution of the present invention is prepared, for example, by filtering a solution having a solid content concentration of 5 to 50% by weight with a filter having a pore size of about 0.2 μm.

When a resist pattern is formed from the chemically amplified resist solution of the present invention, the composition is applied by means such as spin coating, cast coating, or roll coating to, for example, a silicon wafer having a thickness of about 0.2 μm. A resist film is formed by applying it onto a substrate such as a wafer coated with aluminum, and the resist film is irradiated with radiation so as to form a desired pattern. The radiation used at that time depends on the type of the radiation-sensitive acid generator used, i-rays and other ultraviolet rays; KrF excimer lasers and other deep ultraviolet rays; synchrotron radiation and other X-rays; and electron beam and other charged particles. Select and use the line appropriately. When forming a resist pattern using the chemically amplified resist solution of the present invention, a protective film may be provided on the resist film in order to prevent the influence of basic impurities contained in the working atmosphere. Further, in order to improve the apparent sensitivity of the resist film, it is preferable to perform baking after irradiation with radiation.
The heating condition is usually 30 to 200 ° C., preferably 50.
~ 150 ° C.

Next, by developing with an alkali developing solution, a predetermined resist pattern is formed. Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine,
Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8
-Diazabicyclo- [5.4.0] -7-undecene,
An alkaline aqueous solution prepared by dissolving an alkaline compound such as 1,5-diazabicyclo- [4.3.0] -5-nonene to a concentration of usually 1 to 10% by weight, preferably 2 to 5% by weight is used. To be done. Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant can be added to the developer. When using a developing solution consisting of an alkaline aqueous solution as described above,
Generally, it is washed with water after development.

[0065]

EXAMPLES The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. In the examples, various characteristics were evaluated as follows. Mw Tosoh Corp. GPC column (2 G2000H _XL ,
G3000H _XL 1 piece, G4000 _XL 1 piece)
The flow rate was 1.0 ml / min, the elution solvent was tetrahydrofuran, and the column temperature was 40 ° C. Film formation (coating property) The chemically amplified resist solution was spin-coated on a 6-inch silicon wafer and baked at 90 ° C. for 2 minutes, and then the formed resist film was observed. The case where there was no coating unevenness, cloudiness and foreign matter and the surface smoothness was high was defined as good. The sensitivity was defined as the radiation dose at which a line-and-space pattern with a sensitivity of 0.5 μm could be formed as designed. The unit is mJ / cm ² . In order to evaluate the storage stability of the resist solution, the film thickness was calculated by measuring the film thickness of the resist film before and after development by α-step manufactured by Tencor. When the amount of film reduction was 10% or more of the initial coating film thickness, it was determined to be defective.

Synthesis Example 1 30 g of polyhydroxystyrene was dissolved in tetrahydrofuran, 10 g of potassium t-butoxide was added, and di-t-butyl dicarbonate 60 was added at 0 ° C. with stirring.
g was added dropwise and reacted for 4 hours. After the reaction was completed, this solution was dropped into water, and the precipitated resin was dried in a vacuum dryer at 50 ° C.
Dried overnight. The resin obtained has an Mw of 15,000.
From the result of NMR measurement, it was a structure in which 29% of hydrogen atoms of the phenolic hydroxyl group were substituted with t-butoxycarbonyl group. This resin is called resin (I).

Synthesis Example 2 300 g of pt-butoxystyrene, 30 g of styrene and 1.6 g of azobisisobutyronitrile were added to dioxane 3
It was dissolved in 30 and reacted for 12 hours in a nitrogen atmosphere while maintaining the internal temperature at 70 ° C. After the reaction, reprecipitation treatment is performed to remove unreacted monomers, and poly (pt-butoxystyrene-
A styrene) copolymer resin was obtained. Subsequently, this resin was hydrolyzed with an acid to obtain 180 g of a poly (p-hydroxystyrene-styrene) copolymer resin having an Mw of 18,000. When the copolymerization ratio was determined by NMR, it was p-hydroxystyrene: styrene = 85: 15 (molar ratio).
This resin is called resin (II).

Synthesis Example 3 Vinylphenol 20 g, t-butyl acrylate 20
g and 8.5 g of styrene were dissolved in 50 g of dioxane,
After adding 1.0 g of 2,2'-azobisisobutyronitrile and performing bubbling with nitrogen gas for 30 minutes, it heated at 60 degreeC and polymerized for 7 hours, continuing bubbling.
After the polymerization, the solution was coagulated in a large amount of hexane to recover the resin. The operation of dissolving this resin in acetone and then solidifying it again in hexane was repeated several times to completely remove unreacted monomers, and the resin was dried overnight at 50 ° C. under reduced pressure. The obtained resin was white and the yield was 55%. N
As a result of MR analysis, the resin composition was vinylphenol, t-
Butyl acrylate and styrene were copolymerized in a ratio of approximately 2: 2: 1, and Mw was 24,000. This resin is designated as resin (III).

Synthesis Example 4 26 g of vinylphenol and 17 g of t-butyl acrylate
And 50 g of propylene glycol monomethyl ether were added to form a uniform solution, and then bubbling was performed with nitrogen gas for 30 minutes to prepare 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) as a radical polymerization initiator.
1.9 g (2 mol% relative to the total amount of monomers) was added,
While continuing the bubbling, the internal temperature was kept at 40 ° C. and the copolymerization was carried out for 7 hours. After the copolymerization, the resin was solidified by mixing the copolymerization solution with a large amount of hexane. After dissolving this resin in acetone, the operation of coagulating again in hexane was repeated several times to completely remove the unreacted monomers,
The resin was dried under reduced pressure at 50 ° C. The obtained resin was white and the yield was 55%. As a result of NMR analysis, the composition of the resin was that vinylphenol and t-butyl acrylate were copolymerized at a ratio (molar ratio) of 6: 4, and Mw
Was 22,000. This resin is called resin (IV).

Synthesis Example 5 24 g of polyhydroxystyrene was dissolved in 100 ml of acetone, 9.7 g of t-butyl bromoacetate and 7.6 g of potassium carbonate were added, and the mixture was reacted under stirring and reflux for 8 hours. Then, the reaction solution was extracted with ethyl acetate and washed with a 5% by weight aqueous acetic acid solution and water. After the solvent was distilled off under reduced pressure, the resin was dissolved again in acetone and coagulated with a large amount of water to obtain a white resin. The dry weight of the resin was 30 g and the Mw was 12,000. As a result of NMR measurement, 23% of the phenolic hydroxyl group of this resin is t
-It had a structure substituted with a butoxycarbonylmethyl group. This resin is designated as (V).

Synthesis Example 6 15 g of bisphenol A was dissolved in tetrahydrofuran, 2 times the amount of di-t-butyl dicarbonate and 0.3 times the amount of triethylamine were added to the number of moles of all hydroxyl groups, and the mixture was refluxed for 6 hours. It was made to react. Then, the reaction solution was added dropwise to water, and the resulting precipitate was dried in a vacuum dryer at 50 ° C. overnight. Thus, the dissolution control agent (a) represented by the above formula (9) was obtained.

Synthetic Example 7 The same procedure as in Synthetic Example 6 was carried out in the same manner as in Synthetic Example 6, except that the compound represented by the above structural formula (10) in which t-butoxycarbonyl group was a hydrogen atom was used in place of bisphenol A. By carrying out, the dissolution control agent (b) represented by the above formula (10) was obtained.

Examples 1 to 13 and Comparative Examples 1 to 8 Solvents shown in Table 1 or Table 2 were mixed with other components shown in Table 1 or Table 2, and in Examples 1 to 13,
After adding 0.5 parts by weight of 4'-diaminodiphenyl ether (relative to 100 parts by weight of resin) and dissolving uniformly,
The foreign matter was removed by microfiltration with a 0.2 μm filter to obtain a chemically amplified resist solution. The obtained chemically amplified resist solution was spin-coated on a 6-inch silicon wafer and then baked at 100 ° C. for 2 minutes, and the formed resist film having a film thickness of 1 μm was irradiated with radiation through a mask. Here, for radiation irradiation, a KrF excimer laser irradiation device (M
BK-400TL-N) was used. Then at 110 ℃ 2
After baking for 1 minute, the resist pattern was formed by developing with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds at 23 ° C. and then rinsing with water for 30 seconds. The formation of the resist pattern using the chemically amplified resist solution was performed for the same solution immediately after preparation and 30 days after preparation. The obtained results are shown in Tables 3 and 4.

The radiation-sensitive acid generator, dissolution control agent, crosslinking agent and solvent in Tables 1 and 2 are as follows. Radiation-sensitive acid generator : compound represented by the formula (3): compound represented by the formula (4): compound represented by the formula (5): compound represented by the formula (6): formula (6) compound represented by 7): compound dissolution control agent represented by the formula (8) (a): dissolution agent represented by the formula (9) (b): dissolution regulator crosslinking represented by the formula (10) Agent (c): Compound represented by the formula (16) Solvent PGMEP: Propylene glycol monomethyl ether propionate PGEEP: Propylene glycol monoethyl ether propionate EL: Ethyl lactate (ethyl 2-hydroxypropionate) EEP: 3- Ethyl ethoxypropionate PGDME: Propylene glycol dimethyl ether MMP: Methyl 3-methoxypropionate ECA: Ethyl In Table 1, resin (VI) is hydrogenated poly (hydroxystyrene) (trade name PHM-C, Maruzen Petrochemical Co., Ltd.).
Manufactured).

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

The chemically amplified resist solution of the present invention provides a resist film having excellent sensitivity and resolution. In particular, a resist film obtained by applying a large-diameter substrate by a spin coating method has substantially no coating unevenness or cloudiness and its surface is smooth. Further, fine processing can be stably performed, storage stability is excellent, and a good pattern shape is provided. Further, the chemically amplified resist solution of the present invention is i
UV rays such as rays, far UV rays such as KrF excimer laser,
X-rays such as synchrotron radiation and radiation such as charged particle beams such as electron beams can be used to form a chemically amplified resist coating for integrated circuit manufacturing, which is expected to be further miniaturized in the future. It can be used advantageously as a solution.

The chemically amplified resist of the present invention described above in detail, including its preferred embodiments, will be additionally described. 1. A chemically amplified resist solution, which is a solution of a solvent containing propylene glycol alkyl ether propionate as a component of the solvent. 2. 2. The chemically amplified resist solution according to 1 above, wherein the solvent contains 30% by weight or more of propylene glycol alkyl ether propionate. 3. 3. The chemically amplified resist solution as described in 2 above, wherein the solvent contains 50% by weight or more of propylene glycol alkyl ether propionate. 4. 4. The chemically amplified resist solution as described in 3 above, wherein the solvent consists essentially of propylene glycol alkyl ether propionate. 5. The following components (a), (b) and (c) (a) Acid-decomposable group is contained in the polymer chain and is insoluble or hardly soluble in an alkaline developer, and the acid-decomposable by contact with an acid. 1 to 4 which is a solution of an acid-decomposable group-containing resin in which a group is hydrolyzed to become alkali-soluble, (b) a radiation-sensitive acid generator that generates an acid upon irradiation with radiation, and (c) a solvent. The chemically amplified resist solution according to any one of the above. 6. The amount of the component (b) is 0.
The chemically amplified resist solution as described in 5 above, wherein the proportion of the component (c) is 20 to 3,000 parts by weight, and the proportion is 05 to 20 parts by weight.

7. The following (a) component, (b) component, (c)
Component and (d) Component (a) Alkali-soluble resin, (b) Radiation-sensitive acid generator that generates an acid upon irradiation with radiation, (c) Alkali development of the above-mentioned (a) alkali-soluble resin before contact with acid The (a) alkali-soluble resin contained in the dissolution control agent, which controls the solubility in a liquid and is hydrolyzed by the water present in the film when contacted with an acid Decreases or eliminates the effect of controlling the solubility of the alkali developing solution in (a) or (ii) rather accelerates the solubility of the alkali-soluble resin (a) in the alkali developing solution.
5. The chemically amplified resist solution according to any one of 1 to 4 above, which is a solution of a dissolution control agent and (d) a solvent. 8. The component (b) is 0.0 per 100 parts by weight of the component (a).
5 to 20 parts by weight, the component (c) is 5 to 150 parts by weight,
8. The chemically amplified resist solution as described in 7 above, wherein the component (d) is in a proportion of 20 to 3,000 parts by weight.

9. The following (a) component, (b) component, (c)
Component and (d) Component (a) Alkali-soluble resin, (b) Radiation-sensitive acid generator that generates acid upon irradiation with radiation, (c) Acid reacts with the above-mentioned (a) alkali-soluble resin, and The chemically amplified resist solution according to any one of 1 to 4 above, which is a solution of a crosslinking agent that crosslinks a resin and (d) a solvent. 10. The amount of the component (b) is 0.
05 to 20 parts by weight, the component (c) is 5 to 95 parts by weight,
10. The chemically amplified resist solution according to 9 above, wherein the component (d) is in a proportion of 20 to 3,000 parts by weight. 11. 11. The chemically amplified resist solution according to 1 to 10 above, wherein the chemically amplified resist solution is for forming a resist film for forming a resist pattern of a highly integrated circuit on a silicon wafer.

Claims (1)

[Claims] 1. A chemically amplified resist solution, which is a solution of a solvent containing propylene glycol alkyl ether propionate as a component of the solvent.