KR20030076192A - Chemical amplifying type positive resist composition - Google Patents

Abstract

The present invention

Radiation-sensitive acid generators (A),

The resin (B) itself is insoluble or poorly soluble in aqueous alkali solution but soluble in aqueous alkali solution by the action of acid,

Basic compound (C) and

The present invention relates to a chemically amplified positive resist composition containing four components of a compound (D) having a molar extinction coefficient range of 100 to 50000 with respect to light having a wavelength range of 300 to 450 nm, such as a compound of Formula 4 or a compound of Formula 5.

Formula 4

In Formula 4 above,

R ⁹ and R ¹⁰ are each independently an aryl group, and part or all of the hydrogen atoms on the aryl group may be substituted with a hydroxyl group, an alkyl group, an alkoxy group or an alkoxycarbonyl group,

R ¹¹ to R ¹⁶ are each independently a hydrogen atom or an alkyl group.

Formula 5

In Formula 5 above,

R ¹⁷ is an aryl group, and part or all of the hydrogen atoms on the aryl group may be substituted with a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group or an N, N-dialkylamino group,

R ¹⁸ is a hydrogen atom or an alkyl group,

R ¹⁹ and R ²⁰ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group or a benzoyl group.

Description

Chemical amplifying type positive resist composition

The present invention is a resist composition suitable for lithography acting by high-energy radiation such as ultraviolet rays (including g-rays, i-rays, excimer lasers, etc.), electron beams, X-rays or radiant light, and in particular, g-rays and i-rays. It relates to a resist composition suitable for exposure to light.

Lithography process for manufacturing a semiconductor highly integrated circuit or liquid crystal display device by exposing a film of the photoresist composition applied to a substrate to high energy radiation such as ultraviolet rays, electron beams, X-rays or radiated light and forming a predetermined resist pattern after development This is commonly used. And in manufacture of a liquid crystal display element, it is especially preferable that it is high sensitivity and high resolution.

However, in conventional resist compositions composed of novolac resins and naphthoquinonediazide-based photosensitizers used in the manufacture of liquid crystal display devices, it is generally difficult to increase both the sensitivity and the resolution, and increasing the sensitivity tends to reduce the resolution. Has a problem.

In addition, there is a problem that the dimensional uniformity of the surface is often deteriorated by the influence of the reflected light from the base substrate during exposure in the lithography process.

It is an object of the present invention to provide a chemically amplified positive resist composition that provides a resist pattern that is excellent in sensitivity and resolution, hardly affected by reflected light from the base substrate, and has low dimensional variation.

That is, this invention includes the following invention.

<1> radiation-sensitive acid generator (A) (hereinafter, described as component (A)),

The resin (B) itself is insoluble or poorly soluble in aqueous alkali solution, but soluble in aqueous alkali solution by the action of acid (hereinafter referred to as component (B)),

Basic compound (C) (hereinafter referred to as component (C)); and

A chemically amplified positive resist composition containing four components of compound (D) (hereinafter, referred to as component (D)) having a molar extinction coefficient range of 100 to 50000 for light having a wavelength range of 300 to 450 nm.

<2> The composition according to <1>, wherein the component (A) is a compound represented by the following general formula (1).

In Formula 1 above,

R ¹ to R ³ are each independently a hydrogen atom or a hydrocarbon group,

R ⁴ is a hydrocarbon group, provided that at least one hydrogen atom in the hydrocarbon group of R ¹ to R ⁴ is a hydroxyl group, a nitro group, a cyano group, an alkylamino group, an N, N'-dialkylamino group, an alkoxy group, a cycloalkyl octa Period, aryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group or It may be substituted with a halogen atom, at least one of -CH ₂ -group in the hydrocarbon group may be substituted with -C0- group.

<3><2> method, in formula 1, R ¹ is 2-methylphenyl group, and R ² and R ³ is a hydrogen atom, R ⁴ is n- propyl, n- butyl, n- octyl group, a Toluyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group, 2-naphthyl group, benzyl group or chemical formula Group (2), provided that at least one of the hydrogen atoms in the groups R ¹ to R ⁴ is a hydroxyl group, a nitro group, a cyano group, an alkylamino group, an N, N'-dialkylamino group, an alkoxy group, cycloalkyl Oxy group, aryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group Or a composition which may be substituted with a halogen atom.

<4> The component (B) according to any one of <1> to <3>, wherein the phenolic hydroxyl group and the phenolic hydroxyl group are selected from 1-ethoxyethyl group, 1-ethoxypropyl group or 2-tetrahydropyranyl group The composition is a resin having a protected group.

<5> The composition according to <4>, wherein the component (B) is a polyvinylphenol protected by a part of a hydroxyl group with 1-ethoxyethyl group, 1-ethoxypropyl group or 2-tetrahydropyranyl group.

<6> The composition according to <4>, wherein the component (B) is a novolak resin in which a part of the hydroxyl group is protected by 1-ethoxyethyl group, 1-ethoxypropyl group or 2-tetrahydropyranyl group.

<7> The composition according to any one of <1> to <6>, wherein component (C) is an organic ammonium hydroxide compound.

<8> The composition of <7>, wherein the organic ammonium hydroxide compound is an ammonium hydroxide compound of formula (3).

In Formula 3 above,

R ⁵ to R ⁸ are each independently a hydrocarbon group, or R ⁶ and R ⁷ are hydrocarbon groups and R ⁵ and R ⁸ form a ring together with the nitrogen atom to which they are attached to represent a heterocyclic group, provided that R ⁵ to R ⁸ At least one of the hydrogen atoms in the hydroxyl group, nitro group, cyano group, alkylamino group, N, N'- dialkylamino group, alkoxy group, cycloalkyloxy group, aryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, aryl A carbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group or a halogen atom, and a -CH ₂ -group in the hydrocarbon group May be substituted with a -C0- group.

<9> The compound of formula (8), wherein the ammonium hydroxide compound of formula (3) is tetramethyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, tetra-n-hexyl ammonium hydroxide, tetra-n-octyl ammonium hydroxide At least one compound selected from the group consisting of: hydroxide, phenyltrimethyl ammonium hydroxide, 3- (trifluoromethyl) phenyltrimethyl ammonium hydroxide, and choline.

<10> The composition according to any one of <1> to <9>, wherein component (D) is a compound of formula (4).

In Formula 4 above,

R ⁹ and R ¹⁰ are each independently an aryl group, and part or all of the hydrogen atoms on the aryl group may be substituted with a hydroxyl group, an alkyl group, an alkoxy group or an alkoxycarbonyl group,

R ¹¹ to R ¹⁶ are each independently a hydrogen atom or an alkyl group.

<11> The composition according to any one of <1> to <9>, wherein component (D) is a compound of formula (5).

In Formula 5 above,

R ¹⁷ is an aryl group, and part or all of the hydrogen atoms on the aryl group may be substituted with a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group or an N, N-dialkylamino group,

R ¹⁸ is a hydrogen atom or an alkyl group,

R ¹⁹ and R ²⁰ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group or a benzoyl group.

<12> The composition according to <10>, wherein the component (D) is 1,7-bis- (3-methoxy-4-hydroxyphenyl) -1,6-heptadiene-3,5-dione.

<13> The compound of formula 5 according to <11>, wherein component (D) is R ¹⁷ is 3-methoxy-4-hydroxyphenyl group, R ¹⁸ is hydrogen atom and R ¹⁹ and R ²⁰ are ethoxycarbonyl groups Phosphorus composition.

<14> The component (D) is a compound (D) wherein R ¹⁷ is a 3-methoxy-4-hydroxyphenyl group, R ¹⁸ is a hydrogen atom, R ¹⁹ is a cyano group and R ²⁰ is an isopropoxycarbonyl group A composition of formula (5).

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Component (B) in the present invention is a resin which is itself insoluble or poorly soluble in aqueous alkali solution, but which is chemically changed by the action of acid to be soluble in aqueous alkali solution. The said resin introduce | transduces the protecting group which can be isolate | separated by the action of an acid into alkali-soluble resin, such as resin which has a phenol skeleton or resin which has a (meth) acrylic acid skeleton normally.

Examples of such protecting groups include groups in which quaternary carbon such as tert-butyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl and the like are bonded to an oxygen atom; Tetrahydro-2-pyranyl, tetrahydro-2-furyl, 1-ethoxyethyl, 1- (2-methylpropoxy) ethyl, 1- (2-methoxyethoxy) ethyl, 1- (2-acetyl Acetal groups such as oxyethoxy) ethyl, 1- [2- (1-adamantyloxy) ethoxy] ethyl, and 1- [2- (1-adamantanecarbonyloxy) ethoxy] ethyl; Non-aromatics such as 3-oxocyclohexyl, 4-methyltetrahydro-2-pyron-4-yl (derived from mevalonic acid lactone), 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl The residue (non-aromatic cyclic group) of a cyclic compound, etc. are mentioned.

Among these groups, an acetal group is preferable from the viewpoint of low activation energy of the deprotection reaction and small dimension dependence of the resist pattern on temperature during post-exposure baking (PEB). Among the acetal groups, 1-ethoxyethyl group, 1-ethoxypropyl group, and 2-tetrahydropyranyl group are preferable from the viewpoint of easy availability of raw materials.

As the component (B), a resin in which the phenolic hydroxyl group and the phenolic hydroxyl group are protected by 1-ethoxyethyl group, 1-ethoxypropyl group or 2-tetrahydropyranyl group is preferable. For example, some of the hydroxyl groups of polyvinylphenol are protected with 1-ethoxyethyl group, 1-ethoxypropyl group, or 2-tetrahydropyranyl group, or some of the hydroxyl groups of novolak resin are 1-ethoxyethyl groups. Preference is given to resins protected with, 1-ethoxypropyl groups or 2-tetrahydropyranyl groups.

Although the said protecting group is substituted by hydrogen of phenolic hydroxyl group or hydrogen of a carboxyl group, these protecting groups can be introduce | transduced into alkali-soluble resin which has a phenolic hydroxyl group or a carboxyl group by a well-known protecting group introduction reaction. In addition, component (B) can be obtained by copolymerization using an unsaturated compound having a protecting group as one monomer.

In the chemically amplified positive resist composition of the present invention, an alkali-soluble resin may be contained as a binder component in addition to the component (B) within a range that does not impair the effects of the present invention. Novolak resin etc. are mentioned as alkali-soluble resin which may be contained.

Novolak resins are usually obtained by condensing phenolic compounds and aldehydes in the presence of an acid catalyst.

Phenolic compounds that can be used in the production of novolac resins include, for example, phenol, o-, m- or p-cresol, 2,3-, 2,5-, 3,4- or 3,5-xylene Ol, 2,3,5-trimethylphenol, 2-, 3- or 4-tert-butylphenol, 2-3-butyl-4- or 5-methylphenol, 2-, 4- or 5-methylrezo Lecinol, 2-, 3- or 4-methoxyphenol, 2,3-, 2,5- or 3,5-dimethoxyphenol, 2-methoxyresorcinol, 4-tert-butylcatechol, 2-, 3- or 4-ethylphenol, 2,5- or 3,5-diethylphenol, 2,3,5-triethylphenol, 2-naphthol, 1,3-, 1,5- or 1, And polyhydroxytriphenylmethane compounds obtained by condensation of 7-dihydroxynaphthalene, xyleneol and hydroxybenzaldehyde. These phenolic compounds can be used individually or in combination of 2 or more, respectively.

Examples of aldehydes that can be used for the production of novolac resins include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, acrolein and crotonaldehyde; Alicyclic aldehydes such as cyclohexanealdehyde, cyclopentanealdehyde, furfural and furyl acrolein; Benzaldehyde, o-, m- or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4- or 3,5-dimethylbenzaldehyde, o-, m- or aromatic aldehydes such as p-hydroxybenzaldehyde; Aromatic aliphatic aldehydes, such as phenylacetaldehyde and cinnamilaldehyde, etc. are mentioned. These aldehydes can be used individually or in combination of 2 or more as desired, respectively. Among these aldehydes, formaldehyde is preferably used in view of ease of industrial purchase.

As an example of the acid catalyst used for condensation of a phenol type compound and aldehydes, Inorganic acids, such as hydrochloric acid, a sulfuric acid, perchloric acid, phosphoric acid; Organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid and p-toluenesulfonic acid; Divalent metal salts such as zinc acetate, zinc chloride, magnesium acetate and the like. These acid catalysts may be used alone or in combination of two or more. The condensation reaction can be carried out according to a conventional method, for example, at a temperature of 60 to 120 ° C. for about 2 to 30 hours.

The novolak resin obtained by condensation can be subjected to operations such as, for example, fractionation to remove low molecular weight components and narrow the molecular weight distribution so that the high molecular weight component is the main component. Since novolak resins are inexpensive, the cost of the chemically amplified positive resist composition of the present invention obtained can be reduced.

In the chemically amplified positive resist composition of the present invention, component (A) is a substance that is decomposed to generate an acid by acting on radiation of light or an electron beam on the substance itself or on the resist composition containing the substance. The acid generated in component (A) acts on component (B) to separate groups that are unstable in the acid present in component (B).

Examples of the component (A) include an onium salt compound, an s-triazine-based organic halogen compound, a sulfone compound, a sulfonate compound, and the like.

Among these, the compound of the following general formula (1) may be mentioned as a preferred one in view of high absorption around 436 nm (g line) and 365 nm (i line) and high sensitivity, resolution, and tensile resistance after application or after exposure in the resist composition.

Formula 1

In Formula 1 above,

R ¹ to R ³ are each independently a hydrogen atom or a hydrocarbon group,

R ⁴ is a hydrocarbon group, provided that at least one hydrogen atom in the hydrocarbon group of R ¹ to R ⁴ is a hydroxyl group, a nitro group, a cyano group, an alkylamino group, an N, N'-dialkylamino group, an alkoxy group, a cycloalkyl octa Period, aryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group or It may be substituted with a halogen atom, at least one of -CH ₂ -group in the hydrocarbon group may be substituted with -C0- group.

As a hydrocarbon group in R <^1> of Formula 1, a C6-C18 aryl group etc. are preferable. As R <^2> and R <^3> , a hydrogen atom, a C1-C12 alkyl group, etc. are preferable. Moreover, as a hydrocarbon group of R <^4> , a C1-C12 alkyl group, a C6-C18 aryl group, etc. are preferable.

When R <^1> -R <^4> is a hydrocarbon group substituted by the halogen atom, a fluorine atom, a chlorine atom, a boron atom, etc. are mentioned as a halogen atom.

As the compound of the formula (1), for example, in formula (1), R ¹ is a 2-methylphenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an n-propyl group, n-butyl group, n-octyl group, Toluyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group, 2-naphthyl group, benzyl group or chemical formula (2), provided that at least one of the hydrogen atoms in the groups of R ¹ to R ⁴ is a hydroxyl group, a nitro group, a cyano group, an alkylamino group, an N, N'-dialkylamino group, an alkoxy group, cycloalkyl Oxy group, aryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group Or a compound which may be substituted with a halogen atom. .

The compound of Formula 1 and other radiation sensitive acid generators, such as an onium salt compound, an s-triazine type organic halogen compound, a sulfone compound, and other sulfonate compounds, can be used together. Also in this case, it is preferable to contain 10% by weight or more of the total amount of the radiation-sensitive acid generator, more preferably 25% by weight or more.

Examples of sulfonate compounds other than the onium salt compound, the s-triazine-based organic halogen compound, the sulfone compound, and the compound of the general formula (1) include the following compounds.

Diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium hexafluoroantimonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, bis (4-tertiary -Butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluoroantimonate, Bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate,

Triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, 4-methylphenyldiphenylsulfonium perfluorobutanesulfonate, 4-methylphenyldiphenyl Sulfonium perfluorooctanesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, p-trildiphenylsulfonium trifluor Romethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsul Phosphorous hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphthoylmethyl) thioranium hexafluoroantimonate, 1- (2-naphthoylmethyl) Tioranium trifluoromethanesulphone Hydrate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate,

2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloro Rhomethyl) -1,3,5-triazine, 2- (benzo [d] [1,3] dioxolan-5-yl) -4,6-bis (trichloromethyl) -1,3,5- Triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl)- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5- Triazine, 2- (2,4-dimethoxystyryl)

-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-tri Azine, 2- (4-butoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-pentyloxystyryl) -4,6-bis ( Trichloromethyl) -1,3,5-triazine,

1-benzoyl-1-phenylmethyl p-toluenesulfonate (common name benzointosylate), 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonate (common name α-methylolbenzointosylate) , 1,2,3-benzenetoluyl trimethanesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, 4-nitrobenzyl p-toluenesulfonate,

Diphenyl disulfone, di-p-tolyl disulfone, bis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis ( 4-tert-butylphenylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, (benzoyl) (phenylsulfonyl) diazo methane,

N- (phenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsul Ponyloxy) -5-norbornene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (10-camphor-sulfonyloxy) naphthalimide And

4-methoxy-α-[[[(4-methylphenyl) sulfonyl] oxy] imino] benzeneacetonitrile and the like.

As a basic compound (C) in a chemically amplified positive resist composition of this invention, a nitrogen containing basic compound is mentioned, For example, an organic ammonium hydroxide compound and amines are mentioned.

Among these, the ammonium hydroxide compound of following formula (3) is mentioned.

In Formula 3 above,

R ⁵ and R ⁸ are each independently a hydrocarbon group, or R ⁶ and R ⁷ are hydrocarbon groups and R ⁵ and R ⁸ represent a heterocyclic group which together with the nitrogen atom to which they are attached form a ring, provided that R ⁵ to R ⁸ At least one of the hydrogen atoms in the hydroxyl group, nitro group, cyano group, alkylamino group, N, N'-dialkylamino group, alkoxy group, cycloalkyloxy group, aryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, aryl A carbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group or a halogen atom, and in the hydrocarbon group, a -CH ₂ -group -CO- group can be substituted.

As the (substituted) hydrocarbon group in R ⁵ to R ⁸ of the general formula (3), methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n -Hexyl group, cyclohexyl group, n-octyl group, 2-hydroxyethyl group, phenyl group, 3- (trifluoromethyl) phenyl group, etc. are mentioned. Preferred embodiments include tetramethyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, tetra-n-hexyl ammonium hydroxide, tetra-n-octyl ammonium hydroxide, phenyltrimethyl ammonium hydroxide, 3- ( Trifluoromethyl) phenyltrimethyl ammonium hydroxide, trimethyl ammonium hydroxide (common name choline), etc. are mentioned.

As a heterocyclic group when R <^5> and R <^8> forms the ring with the nitrogen atom to which they couple | bonded, a pyrrolidine ring group, an oxo pyrrolidine ring group, a piperidine ring group, an azepine ring group, etc. are mentioned, for example. Specific examples thereof include the following compounds.

, ,

, , , , ,

And

As amines, the following compounds are mentioned, for example.

,

,

, ,

, ,

, ,

And

[here,

R ²¹ and R ²² are each independently a hydrogen atom, preferably an alkyl group having 1 to 6 carbon atoms, preferably a cycloalkyl group having 5 to 10 carbon atoms, or preferably an aryl group having 6 to 10 carbon atoms (wherein the alkyl group, One or more of the hydrogen atoms on the cycloalkyl group or the aryl group may be substituted by a hydroxyl group, an amino group or an alkoxy group having 1 to 6 carbon atoms, and the hydrogen atoms on the amino group described above may be substituted by an alkyl group having 1 to 4 carbon atoms. )

R ²³ , R ²⁴ and R ²⁵ are each independently a hydrogen atom, preferably an alkyl group having 1 to 6 carbon atoms, preferably a cycloalkyl group having 5 to 10 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms, or preferably Is an alkoxy group having 1 to 6 carbon atoms (wherein at least one of the hydrogen atoms on the alkyl group, cycloalkyl group, aryl group or alkoxy group may be substituted by hydroxyl group, amino group or alkoxy group having 1 to 6 carbon atoms, and the amino group The hydrogen atom may be substituted by an alkyl group having 1 to 4 carbon atoms),

R ²⁶ is preferably an alkyl group having 1 to 6 carbon atoms, or preferably a cycloalkyl group having 5 to 10 carbon atoms (wherein at least one of the hydrogen atoms on the alkyl group or cycloalkyl group is a hydroxyl group, an amino group or a May be substituted by an alkoxy group, and the hydrogen atom on the amino group may be substituted by an alkyl group having 1 to 4 carbon atoms),

A is preferably an alkylene group, carbonyl group, imino group, -S- group or -S-S- group having 2 to 6 carbon atoms,

The alkyl group and the alkoxy group in R ²¹ to R ²⁶ may be linear or branched chain]

Moreover, the hindered amine compound which has the piperidine skeleton of Unexamined-Japanese-Patent No. 11-52575 is mentioned.

Component (D) is a compound having a molar extinction coefficient range of 100 to 50000 for light having a wavelength range of 300 to 450 nm, preferably a compound having 4000 to 50000, more preferably 4000 to 40000.

Here, the molar extinction coefficient is a number indicating how much light the material absorbs per mole. Lambert Beer's Law is that the intensity of light from I ₀ to I is absorbed between light through a material layer of thickness b (light path length) b, containing c mole of material per liter. By the formula 1, but the molar extinction coefficient is a value defined by κ in the formula (refer to page 185 of the Chemical Metabolism 8, published on March 15, 1984). .

As the component (D), a compound of the formula (4) or (5) is preferable.

Formula 4

In Formula 4 above,

R ⁹ and R ¹⁰ are each independently an aryl group, and part or all of the hydrogen atoms on the aryl group may be substituted with a hydroxyl group, an alkyl group, an alkoxy group or an alkoxycarbonyl group,

R ¹¹ to R ¹⁶ are each independently a hydrogen atom or an alkyl group.

Formula 5

In Formula 5 above,

R ¹⁷ is an aryl group, and part or all of the hydrogen atoms on the aryl group may be substituted with a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group or an N, N-dialkylamino group,

R ¹⁸ is a hydrogen atom or an alkyl group,

R ¹⁹ and R ²⁰ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group or a benzoyl group.

Among the compounds of the general formula (4) or (5), the following are particularly preferred.

1,7-bis- (3-methoxy-4-hydroxyphenyl) -1,6-heptadiene-3,5-dione (collectively crucumin), 1,7-bis- (3-methoxy-4 -Acetoxyphenyl) -1,6-heptadiene-3,5-dione, 1- (3-methoxy-4-hydroxyphenyl) -7- (3-methoxy-4-acetoxyphenyl) -1 , 6-heptadiene-3,5-dione, 1,7-bis- (3-methyl-4-hydroxyphenyl) -1,6-heptadiene-3,5-dione, 1,7-bis- ( 3-methyl-4-acetoxyphenyl) -1,6-heptadiene-3,5-dione, 1- (3-methyl-4-hydroxyphenyl) -7- (3-methyl-4-acetoxyphenyl ) -1,6-heptadiene-3,5-dione, 1,7-bis- (3-methoxy-4-hydroxyphenyl) -1,2,6,7-tetramethyl-1,6-hepta Diene-3,5-dione, 1,7-bis- (3-methoxy-4-acetoxyphenyl) -1,2,6,7-tetramethyl-1,6-heptadiene-3,5-dione , 1- (3-methoxy-4-hydroxyphenyl) -7- (3-methoxy-4-acetoxyphenyl) -1,2,6,7-tetramethyl-1,6-heptadiene-3 , 5-dione, 1,7-bis- (3-methoxy-4-hydroxyphenyl) -4,4-dimethyl-1,6-heptadiene-3,5-dione, 1,7-bis- ( 3-methoxy-4-acetoxyphenyl) -4,4- Dimethyl-1,6-heptadiene-3,5-dione, 1- (3-methoxy-4-hydroxyphenyl) -7- (3-methoxy-4-acetoxyphenyl) -4,4-dimethyl -1,6-heptadiene-3,5-dione,

α-cyanocinnamic acid methyl, α-cyanocinnamic acid ethyl, α-cyanocinnamic acid isopropyl, α-cyanocinnamic acid-n-butyl, 4-hydroxy-α-cyanocinnamic acid methyl, 4-hydroxy-α Ethyl cyanocinnamic acid, 4-hydroxy-α-cyanocinnamic acid isopropyl, 4-hydroxy-α-cyanocinnamic acid-n-butyl, 4-ethoxy-α-cyanocinnamic acid methyl, 4-ethoxy ethyl α-cyanocinnamic acid, 4-ethoxy-α-cyanocinnamic acid isopropyl, 4-ethoxy-α-cyanocinnamic acid-n-butyl, 2,4-hydroxy-α-cyanocinnamic acid, 2,4-hydroxy-α-cyanocinnamic acid ethyl, 2,4-hydroxy-α-cyanocinnamic acid isopropyl, 2,4-hydroxy-α-cyanocinnamic acid-n-butyl, 3-methoxy 4-Hydroxy-α-cyanocinnamic acid methyl, 3-methoxy-4-hydroxy-α-cyanocinnamic acid ethyl, 3-methoxy-4-hydroxy-α-cyanocinnamic acid isopropyl, 3- Methoxy-4-hydroxy-α-cyanocinnamic acid-n-butyl, 4- (N, N'-diethylami ) -α-cyanocinnamic acid methyl, 4- (N, N'-diethylamino) -α-cyanocinnamic acid ethyl, 4- (N, N'-diethylamino) -α-cyanocinnamic acid isopropyl, 4- (N, N'-diethylamino) -α-cyanocinnamic acid-n-butyl, 4-hydroxy-α-ethoxycarbonylcinnamic acid methyl, 4-hydroxy-α-ethoxycarbonylcinnamic acid ethyl , 4-hydroxy-α-ethoxycarbonylcinnamic acid isopropyl, 4-hydroxy-α-ethoxycarbonylcinnamic acid-n-butyl, 2,4-dihydroxy-α-ethoxycarbonylcinnamic acid, 2,4-dihydroxy-α-ethoxycarbonylcinnamic acid ethyl, 2,4-dihydroxy-α-ethoxycarbonylcinnamic acid isopropyl, 2,4-dihydroxy-α-ethoxycarbonylcinnamic acid -n-butyl, 3-methoxy-4-hydroxy-α-methoxydicarbonylcinnamic acid methyl, 3-methoxy-4-hydroxy-α-ethoxycarbonylcinnamic acid ethyl, 3-methoxy-4 -Hydroxy-α-ethoxycarbonylcinnamic acid isopropyl, 3-methoxy-4-hydroxy-α-ethoxycarbonylcinnamic acid-n-part , 2-hydroxy-4- (N, N'-dimethylamino) -α-ethoxycarbonylcinnamic acid methyl, 2-hydroxy-4- (N, N'-dimethylamino) -α-ethoxycarbonylcin Ethyl hexane, 2-hydroxy-4- (N, N'-diethylamino) -α-ethoxycarbonylcinnamic acid methyl, 2-acetoxy-4- (N, N'-diethylamino) -α- Ethyl ethoxycarbonylcinnamic acid, 1,1-dicyano-2- (4-hydroxyphenyl) ethyl, 1-cyano-1-benzoyl-2- (3-methoxy-4-hydroxyphenyl) ethylene, 1-cyano-1-methoxycarbonyl-2- (1-naphthyl) ethylene, 1-cyano-1-ethoxycarbonyl-2- (1-naphthyl) ethylene, 1-cyano-1 -Methoxycarbonyl-2- (2-hydroxy-1-naphthyl) ethylene, 1-cyano-1-ethoxycarbonyl-2- (2-hydroxy-1-naphthyl) ethylene and the like.

These can be used individually or in combination of 2 or more types.

Among them, 1,7-bis- (3-methoxy-4-hydroxyphenyl) -1,6-heptadiene-3,5-dione and 3-methoxy-4-hydroxy-α-ethoxycarbonylcin Ethyl acetate and 3-methoxy-4-hydroxy-α-cyanocinnamic acid isopropyl are particularly preferably used.

It is preferable that the chemically amplified positive resist composition of the present invention contains the component (A) in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the component (B).

Moreover, it is preferable to contain a component (C) in 0.001-10 weight part with respect to 100 weight part of components (B).

Moreover, it is preferable to contain a component (D) in 0.001-20 weight part with respect to 100 weight part of component (B).

The chemically amplified positive resist composition of the present invention may, if necessary, contain various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers and dyes in a range that does not impair the effects of the present invention. .

The chemically amplified positive resist composition of the present invention is usually a resist composition in the state in which each component of the above (A) to (D) is dissolved in a resist solvent, and spins according to a conventional method on a substrate such as a silicon wafer. It is applied by a method such as coating. The resist solvent used here should just melt | dissolve each component, provide a suitable drying rate, and provide a uniformly smooth coating film after a solvent evaporates.

As a resist solvent, For example, glycol ether ester, such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate; Esters such as ethyl lactate, butyl acetate, amyl acetate or ethyl pyruvate; Ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; Alcohol, such as 3-methoxy-1- butanol, etc. are mentioned. These resist solvents can be used individually or in combination of 2 or more, respectively.

The resist coated on the substrate and dried is usually subjected to an exposure treatment for patterning, followed by heat treatment (PEB) to promote the deprotecting group reaction, and then developed with an alkaline developer. Alkaline developer used herein is a variety of alkaline aqueous solution used in the art, but in general, an aqueous solution of tetramethyl ammonium hydroxide or (2-hydroxyethyl) trimethyl ammonium hydroxide (common name choline) is often used.

Example

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. In addition,% and part which show content-usage-amount in an example are a basis of weight unless there is particular notice. In addition, a weight average molecular weight (Mw) and polydispersity (Mw / Mn) are the values measured by the gel permeation chromatography using polystyrene as a reference material.

Synthesis Example 1 Synthesis of Partial 1-Ethoxyethylate of Polyhydroxystyrene

400 g of poly (p-hydroxystyrene) (3.33 mol as p-hydroxystyrene unit) and 63.0 mg (0.333 mmol) of p-toluenesulfonic acid monohydrate were charged into a 5 L four-neck flask and dissolved in 2400 g of methyl isobutyl ketone. Let's do it. 249 g (3.46 mol) of ethylvinyl ether was added dropwise to this solution, followed by reaction at 27 ° C. for 3 hours.

The reaction solution was washed with water using 933 g of ion-exchanged water. All of these water washings were repeated five times, followed by distillation under reduced pressure to distill most of the methyl isobutyl ketone. Next, 3500 g of propylene glycol monomethyl ether acetate is added and distillation under reduced pressure is carried out to remove water and residual methyl isobutyl ketone by azeotroping with propylene glycol monomethyl ether acetate to obtain a propylene glycol monomethyl ether acetate solution.

The resulting liquid is a solution of a resin in which the hydroxyl group of poly (p-hydroxystyrene) is partially 1-ethoxyethyl ether and 48% of the hydroxyl groups are 1-ethoxy as a result of analyzing ¹ H-NMR of this resin. Ethyl etherified.

Such resin is referred to as resin B1.

Synthesis Example 2: Synthesis of m-cresol novolac resin from low molecular weight

Into a 1 L four-necked flask equipped with a reflux tube, a stirrer, and a thermometer, 218.3 g of m-cresol, 10.2 g of oxalic acid dihydrate, 68.7 g of 90% acetic acid, and 203 g of methyl isobutyl ketone were heated up to 80 ° C. and 37% form 143.2 g of aqueous aldehyde solution is added dropwise for 1 hour. Then, the temperature is raised to reflux temperature and kept at reflux for 12 hours. The obtained reaction solution was diluted with methyl isobutyl ketone, washed with water and dehydrated to obtain a 36.8% methyl isobutyl ketone solution of novolac resin. 612 g of this resin solution was added to a 5 L bottom discharge flask and diluted with 1119 g of methyl isobutyl ketone. Then, 1232 g of n-heptane was added thereto, stirred at 60 DEG C, allowed to stand, followed by separating a lower novolak resin solution. To obtain.

This novolak resin solution is diluted with propylene glycol methylether acetate and then concentrated to give a propylene glycol methylether acetate solution of novolak resin. Such resin is referred to as resin B2.

As a result of measuring this resin with polystyrene as a standard material and measuring by gel permeation chromatography (GPC), the area ratio of the molecular weight 1,000 or less with respect to the total pattern area from which the unreacted monomer was removed is 3.28%. The weight average molecular weight is 9079.

Next, a resist composition is prepared and evaluated using the raw material described below in addition to each resin obtained by the above synthesis example.

Component (A1): (5-Toluylsulfonyloxyimino-5H-thiophen-2-yridine)-(2-methylphenyl) acetonitrile

Component (C1): Tetrabutyl Ammonium Hydroxide

Component (D1): 1,7-bis- (3-methoxy-4-hydroxyphenyl) -1,6-heptadiene-3,5-dione mole [molar extinction coefficient at wavelength 436 nm is 18200.]

Component (D2): 3-methoxy-4-hydroxy-α-cyanocinnamic acid isopropyl [molar extinction coefficient at wavelength 365nm is 21500]

In addition, the molar extinction coefficient is such that the concentration of component (D1) and component (D2) is in the range of 0.00003 to 0.00004 mol / L using a DU 640 (manufactured by Beckman Instruments, Inc.) instrument. A methanol solution is prepared and measured in a container with an optical path length of 1 cm.

Examples 1 and 2, Comparative Examples 1 and 2

6.75 parts (in terms of solids) of resin B1 and B2 were mixed, 0.1 part of component (A1), 0.015 part of basic compound (C1), and 0.25 parts of component (D1) only in Examples 1 and 2, respectively (Example 1) and 0.25 parts of component (D2) (Example 2) were added (in Comparative Examples 1 and 2, neither component (D1) nor component (D2) was added) and they were dissolved in 42 parts of propylene glycol monomethylether acetate. Let's do it. The solution obtained is filtered with a fluorine resin filter having a pore diameter of 0.5 µm to prepare a resist.

The above-mentioned resist is applied to a silicon wafer treated with hexamethyldisilazane such that the thickness of the film after drying is a value shown in Table 1 using a rotary coater. Prebaking after application of the resist is carried out at 90 ° C. for 60 seconds using a heating plate. Thus, in Example 1 and Comparative Example 1, a reduced projection exposure machine having an exposure wavelength of 436 nm (g-ray) on a wafer on which a resist was formed ("NSR-1755g7A" manufactured by Nikon Corporation, NA = 0.54) In Example 2 and Comparative Example 2, a line-and-space pattern (line and space pattern) was used using a reduced projection exposure machine (NSR-2005i9C, NA = 0.57 manufactured by Nikon Corporation) having an exposure wavelength of 365 nm (i-line). and space pattern) are exposed by changing the exposure amount in stages. Next, a post exposure bake (PEB) was performed at 110 ° C. for 60 seconds using a heating plate, followed by a 2.38% aqueous tetramethyl ammonium hydroxide solution [Sumitomo Chemical Co., Ltd. (Sumitomo Chemical Co., Ltd.). Paddle development for 60 seconds with developer SOPD. The pattern after development is observed with a scanning electron microscope, and the sensitivities, dimensional variation and resolution according to the change of the film thickness are investigated by the method described below. The results are shown in Table 1.

Effectiveness Sensitivity: First, Example 1 and Comparative Example 1 (g line) were evaluated at a film thickness of 1.54 μm, and Example 2 and Comparative Example 2 (i line) were evaluated at a film thickness of 1.49 μm. A line and space pattern of 1.0 mu m is represented by an exposure amount of 1: 1.

Variation in dimension due to change in thickness of the film: In the exposure dose at the effective sensitivity, the film thickness is taken as the value shown in Table 1, and the dimension when the film thickness is varied is shown.

Resolution: The minimum dimension of the line-and-space pattern separated by the exposure amount of the effective sensitivity.

number Film thickness (㎛) Exposure amount (msec) Dimension (μm) Resolution (μm) Example 1 Example 2 1.541.611.491.54 1351359292 1.000.931.000.95 0.410.45 Comparative Example 1 Comparative Example 2 1.541.611.491.54 165165158158 1.000.861.000.88 0.530.65

According to the chemically amplified positive resist composition of the present invention, it is possible to obtain a resist pattern having low sensitivity and low dimensional variation while maintaining high sensitivity and high resolution.

Claims (14)

Radiation-sensitive acid generators (A), The resin (B) itself is insoluble or poorly soluble in aqueous alkali solution but soluble in aqueous alkali solution by the action of acid, Basic compound (C) and A chemically amplified positive resist composition containing four components of compound (D) having a molar extinction coefficient range of 100 to 50000 for light having a wavelength range of 300 to 450 nm. The composition of claim 1 wherein component (A) is a compound of formula (I): Formula 1 In Formula 1 above, R ¹ to R ³ are each independently a hydrogen atom or a hydrocarbon group, R ⁴ is a hydrocarbon group, provided that at least one hydrogen atom in the hydrocarbon group of R ¹ to R ⁴ is a hydroxyl group, a nitro group, a cyano group, an alkylamino group, an N, N'-dialkylamino group, an alkoxy group, a cycloalkyl octa Period, aryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group or It may be substituted with a halogen atom, at least one of -CH ₂ -group in the hydrocarbon group may be substituted with -C0- group. The compound according to claim 2, wherein in Formula 1, R ¹ is a 2-methylphenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is n-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group, 2-naphthyl group, benzyl group or formula (2), provided that at least one of the hydrogen atoms in the groups of R ¹ to R ⁴ is a hydroxyl group, a nitro group, a cyano group, an alkylamino group, an N, N'-dialkylamino group, an alkoxy group, cycloalkyl Oxy group, aryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group Or a composition which may be substituted with a halogen atom. The component (B) according to any one of claims 1 to 3, wherein the phenolic hydroxyl group and the phenolic hydroxyl group are protected by 1-ethoxyethyl group, 1-ethoxypropyl group or 2-tetrahydropyranyl group. The composition which is resin which has group. The composition according to claim 4, wherein component (B) is a polyvinylphenol wherein a part of the hydroxyl group is protected by 1-ethoxyethyl group, 1-ethoxypropyl group or 2-tetrahydropyranyl group. The composition according to claim 4, wherein component (B) is a novolak resin in which a part of the hydroxyl group is protected by 1-ethoxyethyl group, 1-ethoxypropyl group or 2-tetrahydropyranyl group. The composition according to any one of claims 1 to 6, wherein component (C) is an organic ammonium hydroxide compound. 8. The composition of claim 7, wherein the organic ammonium hydroxide compound is an ammonium hydroxide compound of formula (3). Formula 3 In Formula 3 above, R ⁵ to R ⁸ are each independently a hydrocarbon group, or R ⁶ and R ⁷ are a hydrocarbon group and R ⁵ and R ⁸ form a ring together with the nitrogen atom to which they are attached to represent a heterocyclic group, provided that R ⁵ to R ⁸ At least one of the hydrogen atoms in the hydroxyl group, nitro group, cyano group, alkylamino group, N, N'- dialkylamino group, alkoxy group, cycloalkyloxy group, aryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, aryl A carbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group or a halogen atom, and a -CH ₂ -group in the hydrocarbon group May be substituted with a -C0- group. The compound of claim 8, wherein the ammonium hydroxide compound of formula 3 is tetramethyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, tetra-n-hexyl ammonium hydroxide, tetra-n-octyl ammonium hydroxide, At least one compound selected from phenyltrimethyl ammonium hydroxide, 3- (trifluoromethyl) phenyltrimethyl ammonium hydroxide, and choline. The composition according to any one of claims 1 to 9, wherein component (D) is a compound of formula (4). Formula 4 In Formula 4 above, R ⁹ and R ¹⁰ are each independently an aryl group, and part or all of the hydrogen atoms on the aryl group may be substituted with a hydroxyl group, an alkyl group, an alkoxy group or an alkoxycarbonyl group, R ¹¹ to R ¹⁶ are each independently a hydrogen atom or an alkyl group. The composition according to any one of claims 1 to 9, wherein component (D) is a compound of formula (5). Formula 5 In Formula 5 above, R ¹⁷ is an aryl group, and part or all of the hydrogen atoms on the aryl group may be substituted with a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group or an N, N-dialkylamino group, R ¹⁸ is a hydrogen atom or an alkyl group, R ¹⁹ and R ²⁰ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group or a benzoyl group. The composition of claim 10 wherein component (D) is 1,7-bis- (3-methoxy-4-hydroxyphenyl) -1,6-heptadiene-3,5-dione. 12. The composition of claim 11, wherein component (D) is a compound of formula 5 wherein R ¹⁷ is a 3-methoxy-4-hydroxyphenyl group, R ¹⁸ is a hydrogen atom and R ¹⁹ and R ²⁰ are an ethoxycarbonyl group. 12. The compound of formula (5) according to claim 11, wherein component (D) is R ¹⁷ is a 3-methoxy-4-hydroxyphenyl group, R ¹⁸ is a hydrogen atom, R ¹⁹ is a cyano group and R ²⁰ is an isopropoxycarbonyl group The composition is a compound.