JP2002202610A - Resist material and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material, particularly a chemical amplification positive type resist material having higher sensitivity, resolution, exposure margin and process adaptability than a conventional resist material, ensuring a good pattern shape after exposure and exhibiting superior etching resistance and to provide a pattern forming method. SOLUTION: The resist material contains a high molecular compound containing repeating units in which each acid labile group is decomposed by the action of an acid to increase alkali solubility as well as repeating units of formula (1) (where R1 and R2 are each H, hydroxy, substitutable hydroxyalkyl, linear or branched alkyl, substitutable alkoxy or halogen and (n) is 0 or a positive integer of 1-4) and having a weight average molecular weight of 1,000-500,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultra LSI, which has a significantly high alkali dissolution rate contrast before and after exposure, high sensitivity, high resolution, and excellent etching resistance.
The present invention relates to a resist material such as a chemically amplified positive resist material suitable as a fine pattern forming material for manufacturing.

[0002]

2. Description of the Related Art In recent years,
As the integration and speed of LSIs have been increased and the pattern rules have been required to be finer, far-ultraviolet lithography has been regarded as a promising next-generation fine processing technology. The deep ultraviolet lithography can process 0.5 μm or less, and when a resist material having low light absorption is used, a pattern having a side wall nearly perpendicular to the substrate can be formed.

A recently developed acid-catalyzed chemically amplified positive resist material (Japanese Patent Publication No. 2-27660,
Japanese Patent Application Laid-Open No. 3-27829) utilizes a high-intensity KrF excimer laser as a light source of far ultraviolet rays, and is particularly promising for far ultraviolet lithography having high sensitivity, high resolution, high dry etching resistance, and excellent characteristics. It is expected as a resist material.

[0004] Such chemically amplified positive resist materials include a two-component system comprising a base polymer and an acid generator.
Three-component systems comprising a base polymer, an acid generator and a dissolution inhibitor having an acid labile group are known.

For example, Japanese Patent Application Laid-Open No. Sho 62-115440 discloses a resist material comprising poly-p-tert-butoxystyrene and an acid generator. T in the molecule
a two-component resist material comprising a resin having an tert-butoxy group and an acid generator; A two-component resist material comprising hydroxystyrene and an acid generator has been proposed.

Further, JP-A-6-100488 discloses poly [3,4-bis (2-tetrahydropyranyloxy) styrene], poly [3,4-bis (tert-butoxycarbonyloxy) styrene], A resist material comprising a polydihydroxystyrene derivative such as [3,5-bis (2-tetrahydropyranyloxy) styrene] and an acid generator has been proposed.

However, the base resin of these resist materials has an acid labile group in the side chain, and the acid labile group is decomposed by a strong acid such as a tert-butyl group and a tert-butoxycarbonyl group. In that case, the pattern shape of the resist material is likely to be a T-top shape, while an alkoxyalkyl group such as an ethoxyethyl group is decomposed with a weak acid, so that with the lapse of time from exposure to heat treatment. All of them have problems such as a drawback that the pattern shape is extremely thin, and a bulky group in the side chain, so that heat resistance is lowered and sensitivity and resolution are not satisfactory.

Further, a copolymer of hydroxystyrene and a (meth) acrylic acid tertiary ester is used to achieve higher transparency and adhesion to a substrate, to improve tailing to the substrate, and to improve etching resistance. The following resist materials have been reported (JP-A-3-275149, JP-A-6-275149).
This type of resist material has problems such as heat resistance and poor pattern shape after exposure, and the etching resistance has not been satisfactory. Further, at present, as the resolution increases, the pattern becomes thinner at the same time, and accordingly, a resist material having higher etching resistance is desired.

The present invention has been made in view of the above circumstances,
Resist material that has higher sensitivity and resolution, exposure latitude, process adaptability than conventional resist materials, good pattern shape after exposure, and excellent etching resistance, especially chemically amplified positive resist material And a method for forming a pattern.

[0010]

Means for Solving the Problems and Embodiments of the Invention As a result of intensive studies to achieve the above object, the present inventor has a repeating unit represented by the following general formula (1) or (2). Having a weight average molecular weight of 1,000 to 500,00
The polymer compound of No. 0 is effective as a base resin of a positive resist material, particularly a chemically amplified positive resist material, and the chemically amplified positive resist material containing this polymer compound, an acid generator and an organic solvent is used for forming a resist film. High dissolution contrast, high resolution, high exposure latitude, excellent process adaptability, good pattern shape after exposure, and even better etching resistance. It has been found that it is very effective as a resist material for LSI.

That is, the present invention provides the following resist material and pattern forming method. Claim 1: Having a repeating unit represented by the following general formula (1), and having a weight-average molecular weight of 1,000, including a repeating unit in which an acid labile group is decomposed by the action of an acid to increase solubility in alkali. A resist material comprising a polymer compound having a molecular weight of up to 500,000.

Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom, a hydroxy group, a substituted hydroxyalkyl group, a linear or branched alkyl group, a substituted alkoxy group, or a halogen atom. And a positive integer of from 4 to 4.) Claim 2: having a repeating unit represented by the following general formula (2) and having a weight average molecular weight of 1,000 to 500,000.
A resist material comprising a polymer compound of the formula:

Embedded image ^{(Wherein, R 1, R 2, R} 4 is a hydrogen atom, hydroxy group, optionally substituted hydroxyalkyl group, straight-chain or branched alkyl group, a substitutable alkoxy group, or halogen atom, R ^3, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom, a methyl group, an alkoxycarbonyl group, a cyano group, or a halogen atom, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms. M is a positive integer of 0 or 1 to 4, and m is a positive integer of 0 or 1 to 5. p, q,
s is 0 or a positive number, and r is a positive number. Claim 3: In the formula (2), one or both of R ¹ and R ⁴ is a group represented by the following formulas (3) and (4), and has 4 to 2 carbon atoms.
The linear, branched or cyclic tertiary alkoxy group having 0 carbon atoms and each alkyl group is selected from a trialkylsiloxy group having 1 to 6 carbon atoms and an oxoalkoxy group having 4 to 20 carbon atoms. The resist material as described.

Embedded image (Wherein, R ⁸ , R ⁹ , R ¹¹ , and R ¹² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ¹⁰ represents a 1 to 18 carbon atom. oxygen atom interposed may be monovalent hydrocarbon groups may be the R ⁸ and R ^9, R ⁸ and R ^10, R ⁹ and R ¹⁰ form a ring, when they form a ring R ⁸ , R ⁹ ,
R ¹⁰ is a straight or branched alkylene group having 1 to 18 carbon atoms. R ¹³ represents a linear, branched or cyclic alkyl group having 4 to 40 carbon atoms. A is 0 or 1
Is an integer of up to 5. Claim 4: A chemically amplified positive resist composition comprising (A) an organic solvent, (B) the polymer compound according to claim 1, 2 or 3 as a base resin, and (C) an acid generator. . Claim 5: A chemistry comprising (A) an organic solvent, (B) the polymer compound according to claim 1, 2 or 3 as a base resin, (C) an acid generator, and (D) a dissolution inhibitor. Amplified positive resist material. (6) The chemically amplified positive resist material according to the above (4) or (5), further comprising (E) a basic compound as an additive. Claim 7: a step of applying the resist material according to claim 4, 5 or 6 on a substrate, a step of exposing with a high energy beam or an electron beam via a photomask after a heat treatment, and After the heat treatment, developing using a developing solution.

Hereinafter, the present invention will be described in more detail.
The resist material of the present invention has a repeating unit represented by the following general formula (1) and an acid labile group, and the acid labile group is decomposed by the action of an acid to increase the solubility in alkali. Having a weight average molecular weight of 1,000
A polymer compound insoluble or hardly soluble in an aqueous alkali solution (alkali developer) of 0 to 500,000 is contained as a base resin. In this case, as such a polymer compound,
Examples thereof include those having a repeating unit represented by the following general formula (2).

[0013]

Embedded image

[0014] In the ^{formula, R 1, R 2, R} 4 represents a hydrogen atom, hydroxy group, optionally substituted hydroxyl group, a linear or branched alkyl group, a substitutable alkoxy group, or halogen atom, R ³ , R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom, a methyl group, an alkoxycarbonyl group, a cyano group, or a halogen atom, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms. N is 0 or 1 to 4
And m is a positive integer of 0 or 1 to 5. p, q, and s are 0 or a positive number, and r is a positive number.

Here, examples of the substitutable hydroxyalkyl group for R ¹ , R ² and R ⁴ include a hydroxymethyl group, a trifluoromethylated hydroxymethyl group, a ditrifluoromethylated hydroxymethyl group and the like. R ¹ , R ² , R
^As the linear or branched alkyl group of 4, a methyl group,
Examples thereof include an alkyl group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, such as an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, and a tert-butyl group. Examples of the substitutable alkoxy group include those having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, and specific examples include a methoxy group, an ethoxy group, and an isopropoxy group.

In this case, R ¹ and R ⁴ may be variously selected when they exhibit the function of an acid labile group. Particularly, the groups represented by the following formulas (3) and (4), 4
-20 linear, branched or cyclic tertiary alkoxy groups,
Each alkyl group is preferably a trialkylsiloxy group having 1 to 6 carbon atoms or an oxoalkoxy group having 4 to 20 carbon atoms.

[0017]

Embedded image (Wherein, R ⁸ , R ⁹ , R ¹¹ , and R ¹² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ¹⁰ represents a 1 to 18 carbon atom. A monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group and an aralkyl group which may intervene an oxygen atom, R ⁸ and R ⁹ , R ⁸ and R ¹⁰ , R ⁹ and R ^{9
And 10} may form a ring, and when forming a ring, R ⁸ ,
R ⁹ and R ¹⁰ each represent a linear or branched alkylene group having 1 to 18 carbon atoms. R ¹³ represents a linear, branched or cyclic alkyl group having 4 to 40 carbon atoms. A is 0
Or an integer of 1 to 5. )

Here, as the acid labile group represented by the above formula (3), specifically, a methoxyethyloxy group, an ethoxyethyloxy group, an n-propoxyethyloxy group, an iso-propoxy group with an oxygen atom interposed. Ethyloxy group, n-butoxyethyloxy group, iso-butoxyethyloxy group, tert-butoxyethyloxy group, cyclohexyloxyethyloxy group, methoxypropyloxy group, ethoxypropyloxy group, 1-methoxy-1
-Methyl-ethyloxy group, 1-ethoxy-1-methyl-ethyloxy group, tetrahydropyranyloxy group, tetrahydrofuranyloxy group and the like. On the other hand, examples of the acid labile group of the above formula (4) include a tert-butoxycarbonyloxy group, a tert-butoxycarbonylmethyloxy group, an ethylcyclopentylcarbonyloxy group, an ethylcyclohexylcarbonyloxy group, and a methylcyclopentylcarbonyloxy group. .
Further, as the above trialkylsiloxy group, the number of carbon atoms of each alkyl group such as trimethylsiloxy group, triethylsiloxy group, tert-butyldimethylsiloxy group is 1 to 1.
6 are mentioned. Examples of the oxoalkoxy group having 4 to 20 carbon atoms include a 3-oxocyclohexyloxy group and a group represented by the following formula.

[0019]

Embedded image

When R ¹ , R ² and R ⁴ represent a halogen atom, they include a fluorine atom, a chlorine atom and a bromine atom.

As the alkoxycarbonyl group for R ⁶ ,
Those having 2 to 20 carbon atoms, particularly 2 to 6 carbon atoms, are preferred, and specific examples include a methoxycarbonyl group and a tert-butoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

The alkyl group for R ⁷ may be linear, branched or cyclic, but is preferably a tertiary alkyl group. R
^When the alkyl group ⁷ is a tertiary alkyl group, various selections are made, but groups represented by the following general formulas (5) and (6) are particularly preferred.

[0023]

Embedded image (Wherein, R ¹⁴ represents a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, a cyclopentyl group, a vinyl group,
It is an acetyl group, a phenyl group, a benzyl group or a cyano group, and b is 0 or an integer of 1 to 3. )

[0024]

Embedded image (Wherein, R ¹⁵ is a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, a cyclopentyl group, a vinyl group,
It is a phenyl group, a benzyl group or a cyano group. )

As the cyclic alkyl group of the general formula (5),
A 5- or 6-membered ring is more preferred. As a specific example, 1
-Methylcyclopentyl, 1-ethylcyclopentyl,
1-isopropylcyclopentyl, 1-vinylcyclopentyl, 1-acetylcyclopentyl, 1-phenylcyclopentyl, 1-cyanocyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-isopropylcyclohexyl, 1-vinylcyclohexyl,
Examples include 1-acetylcyclohexyl, 1-phenylcyclohexyl, 1-cyanocyclohexyl, and the like.

As a specific example of the general formula (6), tert
-Butyl group, 1-vinyldimethyl, 1-benzyldimethyl, 1-phenyldimethyl, 1-cyanodimethyl, and the like. Further, as the alkyl group for R ⁷ , 2
-Methyladamantyl, 2-ethyladamantyl, 2-
Groups such as methylnorbornyl and 2-ethylnorbornyl are also preferred. Further, in consideration of the properties of the resist material, in the above formula (2), r is a positive number, p, q, and s are 0 or positive numbers, and preferably satisfy the following formula.

0 <r / (p + q + r + s) ≦ 0.5, more preferably 0.05 <r / (p + q + r + s) ≦ 0.
40. 0 ≦ p / (p + q + r + s) ≦ 0.8, more preferably 0.3 ≦ p / (p + q + r + s) ≦ 0.8
It is. 0 ≦ q / (p + q + r + s) ≦ 0.35. 0 ≦ s / (p + q + r + s) ≦ 0.35.

If q or s becomes 0 and the polymer compound of the above formula (2) does not contain this unit, the alkali dissolution rate contrast is lost and the resolution may be degraded. If the proportion of p is too large, the alkali dissolution rate of the unexposed portion may be too high. r is 0
In such a case, the resolution may be deteriorated or the dry etching resistance may not be improved. By appropriately selecting the values of p, q, r, and s within the above range, it is possible to arbitrarily control the pattern dimension and the pattern shape.

The polymer compound of the present invention must have a weight average molecular weight of 1,000 to 500,000, preferably 2,000 to 30,000. If the weight average molecular weight is too small, the resist material will have poor heat resistance. If the weight average molecular weight is too large, the alkali solubility will decrease, and the tailing phenomenon will easily occur after pattern formation.

Further, in the polymer compound of the present invention,
The molecular weight distribution (Mw / M) of the multi-component copolymer of the above formula (2)
When n) is large, foreign matters are seen on the pattern or the pattern shape is deteriorated after exposure due to the presence of a low molecular weight or high molecular weight polymer. Therefore, as the pattern rule becomes finer, the influence of such molecular weight and molecular weight distribution is likely to increase. It is preferable that the molecular weight distribution is as narrow as 1.0 to 2.0, particularly 1.0 to 1.5.

In order to synthesize these polymer compounds, 1
As one method, an acetoxystyrene monomer, a (meth) acrylic acid tertiary alkyl ester monomer and an indene monomer are heated and polymerized in an organic solvent with a radical initiator added thereto, and the obtained polymer compound is alkali-hydrolyzed in an organic solvent. Decomposition is performed to deprotect the acetoxy group, and a polymer compound of a ternary copolymer of hydroxystyrene, tertiary alkyl (meth) acrylate and indene can be obtained. Examples of the organic solvent used during the polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. As the polymerization initiator,
2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2-azobis (2-methylpropionate), benzoyl peroxide, lauroylper Oxides and the like can be exemplified. Preferably, polymerization can be performed by heating to 50 to 80 ° C. The reaction time is 2 to 100 hours, preferably 5 to 100 hours.
20 hours. As the base at the time of alkali hydrolysis,
Aqueous ammonia, triethylamine and the like can be used. The reaction temperature is -20 to 100 ° C, preferably 0 to 6C.
0 ° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.

Further, after isolating the thus obtained polymer compound, an acid labile group represented by the general formula (3) or (4) is introduced into the phenolic hydroxyl group. Is also possible. For example, it is possible to react a phenolic hydroxyl group of a polymer compound with an alkenyl ether compound under an acid catalyst to obtain a polymer compound in which the phenolic hydroxyl group is partially protected by an alkoxyalkyl group.

At this time, the reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran, and ethyl acetate.
They may be used alone or in combination of two or more. As the acid of the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, p
-Pyridinium toluenesulfonate and the like are preferred. The amount of the acid labile group to be introduced is preferably 0.1 to 10 mol% with respect to 1 mol of the phenolic hydroxyl group of the polymer compound to be reacted. The reaction temperature is -20
To 100 ° C, preferably 0 to 60 ° C, and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.

By reacting a halogenated alkyl ether compound with a polymer compound in the presence of a base, a polymer compound in which a phenolic hydroxyl group is partially protected by an alkoxyalkyl group can be obtained. It is.

At this time, the reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethylsulfoxide, etc., and may be used alone or as a mixture of two or more. As the base, triethylamine, pyridine, diisopropylamine, potassium carbonate and the like are preferable. The amount of the acid labile group to be introduced is 10 to 1 mol of the phenolic hydroxyl group of the polymer compound to be reacted.
Preferably, the amount is at least mol%. The reaction temperature is -50 to 100C, preferably 0 to 60C.
And the reaction time is 0.5 to 100 hours, preferably 1 to 20 hours.

Further, the acid labile group of the above formula (4) can be introduced by reacting a dialkyl dicarbonate compound or an alkoxycarbonylalkyl halide with a polymer compound in a solvent in the presence of a base. The reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethylsulfoxide, etc., and may be used alone or as a mixture of two or more.

As the base, triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate and the like are preferable. The amount of the acid labile group to be introduced is preferably such that it is at least 10 mol% with respect to 1 mol of the phenolic hydroxyl group of the original polymer compound.

[0038] The reaction temperature is from 0 to 100 ° C, preferably from 0 to 60 ° C. The reaction time is 0.2 to 100
Hours, preferably 1 to 10 hours.

Examples of the dialkyl dicarbonate compound include di-tert-butyl dicarbonate and di-tert-amyl dicarbonate. Examples of the alkoxycarbonylalkyl halide include tert-butoxycarbonyl methyl chloride,
tert-amyloxycarbonylmethyl chloride, t
tert-butoxycarbonylmethyl bromide, ter
t-butoxycarbonylethyl chloride and the like. However, it is not limited to these synthesis methods.

The resist material of the present invention is preferably used as a positive type, particularly a chemically amplified positive type, and uses the above-mentioned polymer compound as a base polymer. In this case, the resist material of the present invention comprises: (A) Organic solvent (B) Polymer compound as base resin (C) Acid generator Further, if necessary, (D) dissolution inhibitor (E) Basic compound is preferably added.

Here, in the chemically amplified positive resist composition of the present invention, the organic solvent of the component (A) includes butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, Cyclopentanone, 3-ethoxyethyl propionate, 3-ethoxymethyl propionate, 3-methoxymethyl propionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol,
Methyl pyruvate, ethyl pyruvate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, Examples include, but are not limited to, ethyl lactate, propyl lactate, tetramethylene sulfone, and the like. Particularly preferred are propylene glycol alkyl ether acetate and alkyl lactate. These solvents may be used alone or in combination of two or more. Examples of preferred mixed solvents are propylene glycol alkyl ether acetate and alkyl lactate. In addition, the alkyl group of the propylene glycol alkyl ether acetate in the present invention has 1 to 4 carbon atoms, such as a methyl group, an ethyl group, and a propyl group. Among them, a methyl group and an ethyl group are preferable. Further, this propylene glycol alkyl ether acetate includes a 1,2-substituted product and a 1,3-substituted product, and there are three isomers depending on the combination of substitution positions. However, they may be used alone or in a mixture.

The alkyl group of the above-mentioned alkyl lactate has 1 to 4 carbon atoms, for example, a methyl group, an ethyl group and a propyl group. Among them, a methyl group and an ethyl group are preferred.

When propylene glycol alkyl ether acetate is added as a solvent, 5
It is preferably at least 0% by weight, and when adding the alkyl lactate, it is preferably at least 50% by weight based on the total solvent. When a mixed solvent of propylene glycol alkyl ether acetate and alkyl lactate is used as a solvent, the total amount is preferably 50% by weight or more based on the total solvent. In this case, the proportion of propylene glycol alkyl ether acetate is more preferably 60 to 95% by weight, and the proportion of alkyl lactate is 5 to 40% by weight.
If the amount of propylene glycol alkyl ether acetate is small, there is a problem such as deterioration of coating properties. When the amount of the alkyl lactate is too small, there are problems such as insufficient solubility, increase of particles and foreign substances, and when too much, the viscosity becomes high and the applicability becomes poor, and the storage stability deteriorates. The addition amount of these solvents is 300 to 2,000 parts by weight, preferably 400 to 1,000 parts by weight, based on 100 parts by weight of the solid content of the chemically amplified positive resist material.
The concentration is not limited to this as long as it is possible with an existing film forming method.

As the photoacid generator as the component (C), any compound can be used as long as it is a compound which generates an acid upon irradiation with high energy rays. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-
There are sulfonyloxyimide type acid generators and the like. As described in detail below, these can be used alone or in combination of two or more.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate. As the sulfonium cation, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-tert.
t-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium,
(3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis ( 3,4-
Di-tert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl)
Sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis ( 4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2- Oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium and the like; As the salt, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, Examples include toluenesulfonate, benzenesulfonate, 4- (4-toluenesulfonyloxy) benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, and the like, and sulfonium salts of these combinations. .

The iodonium salt is a salt of an iodonium cation and a sulfonate, such as diphenyliodonium, bis (4-tert-butylphenyl) iodonium,
-Tert-butoxyphenylphenyliodonium,
Aryliodonium cations such as 4-methoxyphenylphenyliodonium and sulfonates as trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,
2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,
-(4-toluenesulfonyloxy) benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, and the like, and an iodonium salt of these combinations.

Examples of the sulfonyldiazomethane include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexyl) Sulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) diazomethane , 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsul Sulfonyl benzoyl diazomethane,
4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, t
bis-sulfonyldiazomethane such as ert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane and sulfonylcarbonyldiazomethane.

Examples of the N-sulfonyloxyimide type photoacid generator include succinimide, naphthalenedicarboxylic acid imide, phthalic acid imide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, and 7-oxabicycloimide. [2.2.1] imide skeleton such as -5-heptene-2,3-dicarboxylic imide and trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2
2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, Combination compounds such as methanesulfonate.

The benzoin sulfonate type photoacid generator includes benzoin tosylate, benzoin mesylate,
Benzoin butane sulfonate and the like can be mentioned.

Examples of pyrogallol trisulfonate type photoacid generators include all of the hydroxyl groups of pyrogallol, phloroglysin, catechol, resorcinol and hydroquinone, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2 -Trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, etc. Embedded image

Examples of the nitrobenzyl sulfonate type photoacid generator include 2,4-dinitrobenzyl sulfonate,
-Nitrobenzylsulfonate, 2,6-dinitrobenzylsulfonate, and as the sulfonate,
Specifically, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate Benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate and the like. A compound in which the nitro group on the benzyl side is replaced with a trifluoromethyl group can also be used in the same manner.

Examples of the sulfone-type photoacid generator include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, and 2,2-bis (phenylsulfonyl) propane. , 2,2-bis (4-methylphenylsulfonyl)
Propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl)
Propiophenone, 2- (cyclohexylcarbonyl)
-2- (p-toluenesulfonyl) propane, 2,4-
Dimethyl-2- (p-toluenesulfonyl) pentane-
3-one and the like.

Examples of the glyoxime derivative type photoacid generator include bis-o- (p-toluenesulfonyl) -α-
Dimethylglyoxime, bis-o- (p-toluenesulfol) -α-diphenylglyoxime, bis-o- (p
-Toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,
3-pentanedione glyoxime, bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis- o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o- (n-butanesulfonyl)
-2,3-pentanedione glyoxime, bis-o-
(N-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime , Bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (t
ert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl)-
α-dimethylglyoxime, bis-o- (cyclohexylsulfonyl) -α-dimethylglyoxime, bis-o
-(Benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl)-
α-dimethylglyoxime, bis-o- (p-tert
-Butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl)
-Α-dimethylglyoxime and the like.

Among these, photoacid generators preferably used include sulfonium salts, bissulfonyldiazomethane,
N-sulfonyloxyimide.

The optimum anion of the generated acid varies depending on the easiness of cleavage of the acid labile group used in the polymer, etc. In general, those having no volatility and those having extremely low diffusivity are selected. In this case, preferred anions are benzenesulfonic acid anion, toluenesulfonic acid anion, 4- (4
-Toluenesulfonyloxy) benzenesulfonic acid anion, pentafluorobenzenesulfonic acid anion,
2,2,2-trifluoroethanesulfonic acid anion,
Nonafluorobutanesulfonic acid anion, heptadecafluorooctanesulfonic acid anion and camphorsulfonic acid anion.

The photoacid generator (C) is added in the chemically amplified positive resist composition of the present invention in an amount of 0 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the solids in the resist composition. Department. The photoacid generators (C) can be used alone or in combination of two or more. Furthermore, a photoacid generator having a low transmittance at the exposure wavelength can be used, and the transmittance in the resist film can be controlled by the amount of addition.

As the dissolution inhibitor of the component (D), a compound having a weight-average molecular weight of 100 to 1,000 and having two or more phenolic hydroxyl groups in the molecule is capable of acid-labile the hydrogen atom of the phenolic hydroxyl group. Average 1 overall
Compounds substituted at a rate of 0 to 100 mol% are preferred.
The compound has a weight average molecular weight of 100 to 1,000.
0, preferably 150 to 800. The compounding amount of the dissolution inhibitor is 0 to 50 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 100 parts by weight based on 100 parts by weight of the base resin.
30 parts by weight, and can be used alone or in combination of two or more. If the amount is too small, the resolution may not be improved. If the amount is too large, the film of the pattern may be reduced, and the resolution may be reduced.

Examples of the dissolution inhibitor suitably used as the component (D) include bis (4- (2'-tetrahydropyranyloxy) phenyl) methane and bis (4-
(2′-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert-butoxyphenyl) methane,
Bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl) methane, bis (4- (1 ′)
-Ethoxypropyloxy) phenyl) methane, 2,2
-Bis (4 '-(2 "-tetrahydropyranyloxy)) propane, 2,2-bis (4'-(2" -tetrahydrofuranyloxy) phenyl) propane, 2,2
-Bis (4'-tert-butoxyphenyl) propane, 2,2-bis (4'-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-te
rt-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) propane, 2,2-bis (4′-
(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) tertbutyl valerate, 4,4
-Tert-butyl bis (4 '-(2 "-tetrahydrofuranyloxy) phenyl) valerate, tert-butyl 4,4-bis (4'-tert-butoxyphenyl) valerate
Butyl, tert-butyl 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valerate, 4,4-
Tertbutyl bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate, tertbutyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate, 4,4-bis (4 ′ -(1 ″ -ethoxypropyloxy) phenyl) tertbutyl valerate, tris (4- (2′-tetrahydropyranyloxy) phenyl) methane, tris (4- (2′-tetrahydrofuranyloxy) phenyl) methane, Tris (4-
tert-butoxyphenyl) methane, tris (4-t
tert-butoxycarbonyloxyphenyl) methane,
Tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1,1,2 −
Tris (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4′-
(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-tris (4′-tert-butoxyphenyl) ethane, 1,1,2-tris (4′-ter
t-butoxycarbonyloxyphenyl) ethane, 1,
1,2-tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 '-(1'-ethoxypropyloxy) phenyl) ethane and the like.

As the basic compound as the component (E), a compound capable of suppressing a diffusion rate when an acid generated from a photoacid generator diffuses into a resist film is suitable. The composition improves the resolution by suppressing the diffusion rate of acid in the resist film, suppresses the sensitivity change after exposure, reduces the dependence on the substrate and environment, and improves the exposure margin and pattern profile. can do.

Examples of the basic compound as the component (E) include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, and carboxy groups. Embedded image, a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

Specifically, as primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tertiary amine
t-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,
Nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified. As secondary aliphatic amines, dimethylamine, diethylamine, di-n
-Propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine,
Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N
-Dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, and the like. Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, and triisopropylamine. , Tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine,
Triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetra Examples include methylethylenediamine, N, N, N ', N'-tetramethyltetraethylenepentamine and the like.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, -Melaniline, 4-methylaniline,
Ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyl toluidine), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., Oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (Eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives. Body, pyridine derivatives (for example,
Pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butyl Pyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine,
1-methyl-2-pyridine, 4-pyrrolidinopyridine,
1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives,
Pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1
H-indazole derivative, indoline derivative, quinoline derivative (for example, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, purine derivative, pteridine derivative, carbazole derivative, phenanthridine Derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives,
Adenine derivatives, adenosine derivatives, guanine derivatives,
Guanosine derivatives, uracil derivatives, uridine derivatives and the like are exemplified.

Examples of the nitrogen-containing compound having a carboxyl group include, for example, aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycyl Leucine,
Leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.). Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid,
-Pyridinium toluenesulfonate and the like are exemplified, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol,
2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol,
-Aminoethanol, 3-amino-1-propanol,
4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1-
[2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-
Pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8
-Hydroxyurolidine, 3-quinuclidinol, 3
-Tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl)
Examples include isonicotinamide. Amide derivatives include formamide, N-methylformamide, N, N
-Dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, one or more selected from basic compounds represented by the following general formula (B) -1 can be added. N (X) _n (Y) _3-n (B) -1 where n = 1, 2 or 3. The side chains X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3. The side chain Y is the same or different and represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may include an ether group or a hydroxyl group. Further, Xs may be bonded to each other to form a ring.

[0065]

Embedded image

Here, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ have 1 to 1 carbon atoms.
4, a linear or branched alkylene group, R ³⁰¹ ,
R ³⁰⁴ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain one or more hydroxy groups, ether groups, ester groups or lactone rings.

R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁶ is
~ 20 linear, branched or cyclic alkyl groups,
It may contain one or more hydroxy groups, ether groups, ester groups or lactone rings.

The compound represented by formula (B) -1 is specifically exemplified below. Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl {Amine, Tris} 2- (1-
Ethoxyethoxy) ethyl} amine, tris {2- (1
-Ethoxypropoxy) ethyl} amine, tris [2-
{2- (2-hydroxyethoxy) ethoxy} ethyl]
Amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.88] hexacosan, 4,7,13,18-tetraoxa-1,10-
Diazabicyclo [8.5.5] eicosan, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-
6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2
-Acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, Tris (2-pivaloyloxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-te
rt-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] Amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl]
Amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine,
N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(Ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2
-Methoxyethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-
(Hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2
-[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-
[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2-
(2-oxopropoxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( 2
-Acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N,
N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2
-(4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2 -(Ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl)
Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2-
(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl]
Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine,
N-methylbis (2-pivaloyloxyxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert
-Butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) Examples thereof include, but are not limited to, -δ-valerolactone.

The basic compound can be used alone or in combination of two or more. The compounding amount is 0 to 100 parts by weight of the solids in the resist material.
A mixture of 2 parts by weight, particularly 0.01 to 1 part by weight, is suitable. If the amount exceeds 2 parts by weight, the sensitivity may be too low.

The chemically amplified positive resist composition of the present invention may further contain a surfactant for improving coating properties.

Examples of the surfactant include, but are not particularly limited to, polyoxyethylene alkyl such as polyoxyethylene lauryl ether, polyoxyethylene steryl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether. Ethers, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers,
Sorbitan monolaurate, sorbitan monopalmitate, sorbitan fatty acid esters such as sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate,
Nonionic surfactants of fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, EFTOP EF301, EF303, EF35
2 (Tochem Products), Mega Fuck F171, F
172, F173 (Dainippon Ink and Chemicals), Florado FC430, FC431 (Sumitomo 3M), Asahigard AG710, Surflon S-381, S-38
2, SC101, SC102, SC103, SC10
4, SC105, SC106, Surfynol E100
4, KH-10, KH-20, KH-30, KH-40
(Asahi Glass) and other fluorochemical surfactants, organosiloxane polymers KP341, X-70-092, X-70-
093 (Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based polyflow No. 75, no. 95 (Kyoeisha Yushi Kagaku Kogyo), among which FC430, Surflon S
-381, Surfynol E1004, KH-20, K
H-30 is preferred. These can be used alone or in combination of two or more.

The amount of the surfactant to be added to the chemically amplified positive resist composition of the present invention is 2 parts by weight or less, preferably 1 part by weight or less based on 100 parts by weight of the solids in the resist composition. .

The chemically amplified positive resist containing (A) the organic solvent of the present invention, (B) the high molecular compound represented by the above general formulas (1) and (2), and (C) an acid generator. When the material is used for manufacturing various integrated circuits, a known lithography technique can be used without any particular limitation.

A substrate (Si, SiO ₂ ,
SiN, SiON, TiN, WSi, BPSG, SO
G, organic antireflection film, etc.), spin coating, roll coating, flow coating, dip coating, spray coating,
Coating is performed by a suitable coating method such as doctor coating so that the coating film thickness is 0.1 to 2.0 μm, and on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably 80 to
Pre-bake at ~ 120 ° C for 1-5 minutes. Next, ultraviolet light, far ultraviolet light, electron beam, X-ray, excimer laser, γ
A desired pattern is exposed through a predetermined mask at a light source selected from radiation, synchrotron radiation and the like, preferably at an exposure wavelength of 300 nm or less. Exposure is 1-20
About 0 mJ / cm ² , preferably 10 to 100 mJ / c
Exposure is preferably performed so as to be about m ² . Post exposure bake (PEB) on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes.

Further, 0.1-5%, preferably 2-3%
Of tetramethylammonium hydroxide (TMAH)
Using a developing solution of an aqueous alkali solution such as 0.1 to 3 minutes,
Preferably, the target pattern is formed on the substrate by developing for 0.5 to 2 minutes by a conventional method such as a dip method, a paddle method, and a spray method. In addition, the resist material of the present invention can be applied to a 193 to 254 nm deep ultraviolet light,
It is most suitable for fine patterning by 57 nm vacuum ultraviolet ray, electron beam, soft X-ray, X-ray, excimer laser, γ-ray, and synchrotron radiation. In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0076]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.

Synthesis Example 1 To a 2 L flask were added 13.3 g of acetoxystyrene, 58.6 g of indene, 8.0 g of 1-ethylcyclopentyl methacrylate, and 80 g of toluene as a solvent. The reaction vessel was cooled to -70 ° C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After raising the temperature to room temperature, A is used as a polymerization initiator.
4.1 g of IBN was added, and the mixture was heated to 60 ° C. and reacted for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C to obtain 57 g of a white polymer. Was. 0.5 L of this polymer in methanol,
The residue was dissolved again in 1.0 L of tetrahydrofuran, and 70 g of triethylamine and 15 g of water were added thereto to perform a deprotection reaction, followed by neutralization with acetic acid. After concentrating the reaction solution, acetone 0.1% was added.
After dissolving in 5 L, the same precipitation, filtration and drying as above were performed,
45 g of a white polymer was obtained.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC, and the following results were obtained. Copolymer composition ratio hydroxystyrene: indene: methacrylic acid 1-ethylcyclopentyl ester = 37.9: 40.8: 2
1.3 Weight average molecular weight (Mw) = 5,500 Molecular weight distribution (Mw / Mn) = 1.72 This is designated as (poly-A).

[Synthesis Example 2] A 2 L flask was charged with 22.7 g of acetoxystyrene, 49.5 g of indene, 7.8 g of 1-ethylcyclopentyl methacrylate, and 80 g of toluene as a solvent. The reaction vessel was cooled to -70 ° C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After raising the temperature to room temperature, A is used as a polymerization initiator.
4.0 g of IBN was added, and the mixture was heated to 60 ° C. and reacted for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water. The obtained white solid was filtered and dried at 60 ° C. under reduced pressure to obtain 59 g of a white polymer. Was. 0.5 L of this polymer in methanol,
The residue was dissolved again in 1.0 L of tetrahydrofuran, and 70 g of triethylamine and 15 g of water were added thereto to perform a deprotection reaction, followed by neutralization with acetic acid. After concentrating the reaction solution, acetone 0.1% was added.
After dissolving in 5 L, the same precipitation, filtration and drying as above were performed,
46 g of a white polymer was obtained.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC measurement, and the following results were obtained. Copolymer composition ratio hydroxystyrene: indene: methacrylic acid 1-ethylcyclopentyl ester = 53.8: 28.8: 1
7.4 Weight average molecular weight (Mw) = 6,500 Molecular weight distribution (Mw / Mn) = 1.75 This is defined as (poly-B).

[Synthesis Example 3] A 3 L flask was charged with 36.8 g of acetoxystyrene, 32.9 g of indene, 10.3 g of 1-ethylcyclopentyl methacrylate, and 70 g of toluene as a solvent. The reaction vessel was cooled to -70 ° C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After the temperature was raised to room temperature, 3.7 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by a reaction for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water. The obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 65 g of a white polymer. Was. This polymer was added to methanol 0.5
L, and redissolved in 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, a deprotection reaction was performed, and the mixture was neutralized with acetic acid. After concentrating the reaction solution, it was dissolved in 0.5 L of acetone, and precipitated, filtered and dried in the same manner as above to obtain 52 g of a white polymer.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC, and the following results were obtained. Copolymer composition ratio hydroxystyrene: indene: methacrylic acid 1-ethylcyclopentyl ester = 63.6: 20.0: 1
6.4 Weight average molecular weight (Mw) = 8,800 Molecular weight distribution (Mw / Mn) = 1.78 This is designated as (poly-C).

Synthesis Example 4 37.8 g of acetoxystyrene, 33.9 g of indene, 8.3 g of t-butyl methacrylate, and 70 g of toluene as a solvent were added to a 2 L flask. The reaction vessel was placed in a nitrogen atmosphere at -70.
C., and deaeration under reduced pressure and nitrogen blowing were repeated three times. After raising the temperature to room temperature, AIBN was used as a polymerization initiator.
8 g was added, the temperature was raised to 60 ° C., and the reaction was performed for 15 hours. The reaction solution was concentrated to half, and 4.5 L of methanol,
The precipitate was precipitated in a mixed solution of 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 68 g of a white polymer. This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, and triethylamine 70
g and 15 g of water were added to carry out a deprotection reaction and neutralized with acetic acid. After concentrating the reaction solution, it was dissolved in 0.5 L of acetone, and the same precipitation, filtration, and drying as described above were performed to obtain 54 g of a white polymer.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC measurement, and the following results were obtained. Copolymer composition ratio hydroxystyrene: indene: t-butyl methacrylate = 63.3: 19.8: 16.9 weight average molecular weight (Mw) = 8,500 molecular weight distribution (Mw / Mn) = 1.73 (Poly-D).

Synthesis Example 5 A 2 L flask was charged with 30.8 g of acetoxystyrene, 117.9 g of indene, and 20 g of toluene as a solvent. The reaction vessel was cooled to -70 ° C under a nitrogen atmosphere, and degassed under reduced pressure and nitrogen
Repeated times. After raising the temperature to room temperature, AI is used as a polymerization initiator.
6.2 g of BN was added, and the mixture was heated to 60 ° C. and reacted for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water. The obtained white solid was filtered and dried at 60 ° C. under reduced pressure to obtain 77 g of a white polymer. Was. This polymer was redissolved in 0.5 L of methanol and 1.0 L of tetrahydrofuran, and 70 g of triethylamine and 15 g of water were added to carry out a deprotection reaction and neutralized with acetic acid. After concentrating the reaction solution, acetone 0.5
L and subjected to the same precipitation, filtration and drying as described above to obtain 52 g of a white polymer. This polymer was dissolved in 500 mL of a tetrahydrofuran solvent, and potassium carbonate was further added.
8 g and 10.2 g of t-butyl chloroacetate were added,
The reaction was performed at room temperature for 10 hours. The reaction solution was treated with acetic acid 5.0
g, precipitated in 4 L of water, and washed twice more with water. The obtained white solid was filtered and dried at 40 ° C. under reduced pressure to obtain 58 g of a white polymer.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC measurement, and the following results were obtained. Copolymer composition ratio hydroxystyrene: indene: pt-butoxycarbonylmethyloxystyrene = 29.0: 62.0:
9.0 weight average molecular weight (Mw) = 4,600 molecular weight distribution (Mw / Mn) = 1.77 This is designated as (poly-E).

Synthesis Example 6 A 2-liter flask was charged with 63 g of 5-hydroxyindene, 20.6 g of 1-ethylcyclopentyl methacrylate, and 5 ml of toluene as a solvent.
0 g was added. The reaction vessel was placed in a nitrogen atmosphere at -70 ° C.
, And vacuum degassing and nitrogen blowing were repeated three times.
After the temperature was raised to room temperature, 4.2 g of AIBN was used as a polymerization initiator.
In addition, the mixture was heated to 60 ° C. and reacted for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water. The obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 61 g of a white polymer. Was.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC measurement, and the following results were obtained. Copolymer composition ratio 5-hydroxyindene: 1-ethylcyclopentyl methacrylate = 71.0: 29.0 Weight average molecular weight (Mw) = 7,100 Molecular weight distribution (Mw / Mn) = 1.70 F).

[Comparative Synthesis Example] The product name and analysis results of a two-component polymer synthesized by the same method as in the above Synthesis Example are shown. Hydroxystyrene: 1-ethylcyclopentyl methacrylate = 71: 29 Weight average molecular weight (Mw) = 16,100 Molecular weight distribution (Mw / Mn) = 1.70 This is designated as (poly-G).

Using a 2 L flask, polyhydroxystyrene (Mw = 11,000, Mw / Mn =
1.08) 40 g was dissolved in 400 mL of tetrahydrofuran, 1.4 g of methanesulfonic acid and 12.3 g of ethyl vinyl ether were added, and the mixture was reacted at room temperature for 1 hour. The reaction was stopped by adding 2.5 g of aqueous ammonia (30%). This reaction solution was crystallized and precipitated using 5 L of acetic acid water, washed twice more with water, and the obtained white solid was filtered and dried under reduced pressure at 40 ° C. to obtain 47 g of a white polymer.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC measurement, and the following results were obtained. Copolymer composition ratio hydroxystyrene: p-ethoxyethoxystyrene =
63.5: 36.5 Weight average molecular weight (Mw) = 13,000 Molecular weight distribution (Mw / Mn) = 1.10 This is designated as (poly-H).

Examples and Comparative Examples Resist materials shown in Tables 1 and 2 were prepared. At that time, the polymer compounds of the resist materials listed in Tables 1 and 2 were poly-A to H shown in the above synthesis examples and comparative synthesis examples, and the other components were performed as follows. PAG1: triphenylsulfonium 4- (4'-methylphenylsulfonyloxy) phenylsulfonate PAG2: diphenylsulfonium 4- (4'-methylphenylsulfonyloxy) phenylsulfonate PAG3: bis (cyclohexylsulfonyl) ) Diazomethane PAG4: bis (2,4-dimethylphenylsulfonyl) diazomethane dissolution inhibitor A: bis (4- (2′-tetrahydropyranyloxy) phenyl) methane basic compound A: tris (2-methoxyethyl) amine Activator A: FC-430 (manufactured by Sumitomo 3M) Surfactant B: Surflon S-381 (manufactured by Asahi Glass Co., Ltd.) Solvent A: propylene glycol methyl ether acetate Solvent B: ethyl lactate

[0093]

[Table 1]

[0094]

[Table 2]

After the obtained resist material was filtered with a 0.2 μm Teflon (registered trademark) filter, the resist solution was spin-coated on a silicon wafer,
It was applied to 0.6 μm. Next, the silicon wafer was baked on a hot plate at 100 ° C. for 90 seconds.
In addition, an excimer laser stepper (Nikon, NSR
Exposure using (2005EXNA = 0.5), 110 ° C.
Bake for 90 seconds (PEB: postexposure)
bake) and development with an aqueous solution of 2.38% tetramethylammonium hydroxide, a positive pattern (Examples 1 to 6, Comparative Examples 1 and 2) could be obtained.

The obtained resist pattern was evaluated as follows. Resist pattern evaluation method: An exposure amount that resolves the top and bottom of a 0.18 μm line and space at a ratio of 1: 1 is defined as an optimum exposure amount (sensitivity: Eop), and the minimum of the separated line and space at this exposure amount The line width was taken as the resolution of the evaluation resist. For the shape of the resolved resist pattern, the cross section of the resist was observed using a scanning electron microscope. In addition, the PED stability of the resist was determined as follows.
Exposure bake) was performed, and the evaluation was made based on the fluctuation value of the line width. The smaller the fluctuation value, the higher the PED stability. Table 3 shows the results of the resist pattern evaluation.

Evaluation method other than pattern evaluation: The dry etching resistance of the resist material after development was evaluated by actually etching using TE8500S manufactured by Tokyo Electron Co., Ltd., and then changing the pattern shape using a scanning electron microscope. When the amount of decrease in film thickness after etching in Comparative Example 2 was set to 1.0, the other resists were represented by relative ratios of the amount of decrease. That is, the smaller the numerical value, the better the etching resistance. The etching was performed under the following conditions. Pressure: 33.3 Pa RF Power: 800 W Etching time: 2 minutes 30 seconds

[0098]

[Table 3]

FIG. 1 shows that the dry etching resistance has a considerable correlation with the ratio of indene in the polymer rather than the structure of the polymer used or the resist composition.

[0100]

According to the present invention, the alkali dissolution rate contrast before and after exposure is significantly high, has high sensitivity and high resolution, and exhibits particularly excellent etching resistance. It is possible to provide a resist material such as a chemically amplified resist material suitable as a fine pattern forming material.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between dry etching resistance and indene ratio.

Continuing on the front page (72) Inventor Osamu Watanabe 28-1 Nishifukushima, Nishi-Jukumura, Nakakushiro-gun, Niigata Shin-Etsu Chemical Co., Ltd. 28-1 Nishifukushima Shin-Etsu Chemical Co., Ltd. New Functional Materials Technology Research Center F-term (reference) 2H025 AA01 AA02 AA04 AA09 AB16 AC01 AC04 AC05 AC06 AC08 AD03 BE00 BG00 BJ04 CC03 CC20 FA03 FA12 FA17 2H096 AA25 BA11 BA20 DA01 EA02 EA03 EA04 EA04 EA06 EA07 FA01 GA08 JA02 JA03 LA16 4J100 AB02Q AB07Q AL03Q AL04Q AL05Q AR09P AR10P BA02P BA02Q BA03P BA03Q BA04P BA04Q BA10P BA10Q BA20P BA20Q BA40P BA40Q BB00P BB00Q CA01 CA03 CA04 CA38 CA01

Claims (7)

[Claims] 1. A compound having a repeating unit represented by the following general formula (1) and having a weight average molecular weight of 1, containing a repeating unit in which an acid labile group is decomposed by the action of an acid to increase solubility in alkali. A resist material comprising a polymer compound having a molecular weight of 000 to 500,000. Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom, a hydroxy group, a substituted hydroxyalkyl group, a linear or branched alkyl group, a substituted alkoxy group, or a halogen atom. It is a positive integer of ４4.) 2. A compound having a repeating unit represented by the following general formula (2) and having a weight average molecular weight of 1,000 to 500,0.
A resist material comprising a high molecular compound which is 00. Embedded image ^{(Wherein, R 1, R 2, R} 4 is a hydrogen atom, hydroxy group, optionally substituted hydroxyalkyl group, straight-chain or branched alkyl group, a substitutable alkoxy group, or halogen atom, R ^3, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom, a methyl group, an alkoxycarbonyl group, a cyano group, or a halogen atom, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms. M is a positive integer of 0 or 1 to 4, and m is a positive integer of 0 or 1 to 5. p, q,
s is 0 or a positive number, and r is a positive number. ) 3. A formula (2), R ^1, one or both of R ⁴ is a compound represented by the following formula (3), a group represented by (4), carbon atoms 4
-20 linear, branched or cyclic tertiary alkoxy groups,
The resist material according to claim 2, wherein each alkyl group is selected from a trialkylsiloxy group having 1 to 6 carbon atoms and an oxoalkoxy group having 4 to 20 carbon atoms. Embedded image (Wherein, R ⁸ , R ⁹ , R ¹¹ , and R ¹² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ¹⁰ represents a 1 to 18 carbon atom. oxygen atom interposed may be monovalent hydrocarbon groups may be the R ⁸ and R ^9, R ⁸ and R ^10, R ⁹ and R ¹⁰ form a ring, when they form a ring R ⁸ , R ⁹ ,
R ¹⁰ is a straight or branched alkylene group having 1 to 18 carbon atoms. R ¹³ represents a linear, branched or cyclic alkyl group having 4 to 40 carbon atoms. A is 0 or 1
Is an integer of up to 5. ) 4. A chemically amplified positive resist composition comprising: (A) an organic solvent; (B) the polymer compound according to claim 1, 2 or 3 as a base resin; and (C) an acid generator. . 5. A composition comprising (A) an organic solvent, (B) the polymer compound according to claim 1, 2 or 3 as a base resin, (C) an acid generator, and (D) a dissolution inhibitor. Chemically amplified positive resist material. 6. The chemically amplified positive resist composition according to claim 4, further comprising (E) a basic compound as an additive. 7. A step of applying the resist material according to claim 4, 5 or 6 on a substrate, a step of exposing with a high energy beam or an electron beam via a photomask after a heat treatment, and And performing a heat treatment, followed by developing using a developer.