JP2002229190A - Positive chemically amplifying resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive chemically amplifying resist composition having high sensitivity and high resolution which can give a square and superior pattern profile and which is excellent in PCD(post coating delay) and PED(post exposure delay) stability and coating property. SOLUTION: The positive chemically amplifying resist composition contains a compound (a) which directly or indirectly produces radicals (A) by irradiation of energy rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-working chemically amplified resist composition, and more particularly to a pattern profile obtained by exposure to an electron beam or X-ray, having high sensitivity and excellent resolution, and further having good stability over time ( The present invention relates to a positive chemically amplified resist composition excellent in PCD, PED). Here PC
D (Post Coating Delay) stability refers to the stability of a coating film when a resist composition is applied to a substrate and left in an irradiation apparatus or outside the apparatus, and PED (Post Exposure).
Delay) stability refers to the stability of a coating film when left in an irradiation device or outside the device until a heating operation is performed after irradiation.

[0002]

2. Description of the Related Art The degree of integration of integrated circuits is increasing, and in the manufacture of semiconductor substrates such as VLSIs, the processing of ultrafine patterns having a line width of less than half a minute is required. It has become. Therefore, a chemically amplified resist is used as a resist material for lithography.

In particular, electron beams or X-rays are positioned as a next-generation or next-next-generation pattern forming technology, and development of a positive resist composition capable of achieving high sensitivity, high resolution, and a rectangular profile is desired.

Further, in the case of a positive chemically amplified resist,
The surface is susceptible to the effects of basic contaminants in the air or the effects of exposure inside and outside the irradiation device (drying of the coating film), making the surface hardly soluble. In the case of a contact hole pattern, there is a problem that the surface has a capping shape (an eave is formed on the contact hole surface). Furthermore, stability over time inside or outside the irradiation device (PCD, PE
D) also deteriorated, resulting in a problem that the pattern dimensions fluctuated.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive chemically amplified resist which has high sensitivity, high resolution, can provide an excellent rectangular pattern profile, and has excellent PCD and PED stability. It is to provide a composition. Another object of the present invention is to provide a positive chemically amplified resist composition having excellent coatability (in-plane uniformity).

[0006]

That is, according to the present invention,
The following positive chemically amplified resist composition is provided to achieve the above object of the present invention.

(1) (a) A positive chemically amplified resist composition comprising a compound which generates a radical (A) directly or indirectly upon irradiation with energy rays.

(2) The positive chemically amplified resist composition according to the above (1), further comprising (b) a compound capable of generating an acid upon irradiation with energy rays.

(3) (e) a resin having a group decomposable by an acid and having increased solubility in an alkali developer due to the action of an acid, or (g) a resin insoluble in water and soluble in an alkali developer The positive chemically amplified resist composition according to the above (1) or (2), comprising a resin.

(4) (f) It contains a low molecular weight dissolution inhibiting compound having a molecular weight of 3,000 or less, which has a group decomposable by an acid and whose solubility in an alkali developing solution is increased by the action of an acid. The positive chemically amplified resist composition according to any one of the above (1) to (3).

(5) The radicals (A) to (4), wherein the radical (A) reacts with the compound (a) which generates an acid upon irradiation with energy rays to generate an acid.
The positive chemically amplified resist composition according to any one of the above.

(6) The compound (a), wherein the compound (a) is at least one selected from the following group:
The positive chemically amplified resist composition according to any one of (1) to (5). Alkyl halide other than fluorine, aryl halide other than fluorine, halogen aralkyl other than fluorine,
Allyl halides other than fluorine (however, in the above alkyl, aryl, aralkyl, and allyl groups, some or all of the hydrogens may be substituted with fluorine), thiol compounds, secondary alcohols, allyls which may have a substituent Alcohols, benzyl alcohols which may have a substituent on the aromatic ring, and their esters, ether compounds, sulfide compounds, disulfide compounds, halogenated silicon compounds, alkoxysilicon compounds, linear, branched or cyclic acetal compounds N- Hydroxyl compound

The preferred embodiments are described below. (7) The compound (b) is represented by the following general formulas (I) to (II)
The positive chemically amplified resist composition according to any one of the above (1) to (6), which comprises at least one of the compounds represented by the following formulas:

[0014]

Embedded image

(Wherein R _{1 to} R ₂₂ are the same or different and are each a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, Or a group -SR _23.
23 represents a linear, branched or cyclic alkyl or aryl group. Further, among R _{1 to} R ₁₂ and R _{13 to} R ₂₂ ,
Two or more may combine to form a ring containing one or more selected from a single bond, carbon, oxygen, sulfur, and nitrogen. X ^- is a sulfonic acid anion. )

(8) X ^- is at least one fluorine atom, a straight-chain, branched or cyclic alkyl group substituted with at least one fluorine atom, and a straight-chain substituted with at least one fluorine atom. , Branched or cyclic alkoxy groups, acyl groups substituted with at least one fluorine atom, acyloxy groups substituted with at least one fluorine atom, sulfonyl groups substituted with at least one fluorine atom, Sulfonyloxy group substituted with at least one fluorine atom, sulfonylamino group substituted with at least one fluorine atom, aryl group substituted with at least one fluorine atom, aralkyl substituted with at least one fluorine atom At least one selected from a group and an alkoxycarbonyl group substituted with at least one fluorine atom. Alkylsulfonic acids having one, benzenesulfonic acid, a chemically amplified positive resist composition according to the, characterized in that the anion of naphthalenesulfonic acid, or anthracenesulfonic acid (7).

(9) The positive chemically amplified resist composition according to any one of the above (1) to (8), further comprising (c) an organic basic compound. (10) The above (1) to (d), further comprising (d) a fluorine-based and / or silicon-based surfactant.
The positive chemically amplified resist composition according to any one of (9).

(11) The positive chemically amplified resist composition according to any one of the above (1) to (10), which mainly comprises propylene glycol monomethyl ether acetate as a solvent. (12) The positive chemically amplified resist composition according to any one of (1) to (11), wherein the energy beam is an electron beam or an X-ray.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The positive chemically amplified resist composition of the present invention will be described below. [I] (a) A compound that directly or indirectly generates a radical (A) upon irradiation with an energy ray (also referred to as a component (a) or a compound of (a)). Represents ultraviolet rays, electron beams or X-rays.

Directly generating a radical means that the compound molecule generates a radical by a reaction involving only one molecule upon irradiation with an electron beam or X-ray, and indirectly generating a radical means that the compound molecule generates a radical. It means that a compound molecule generates a radical by another molecule of the compound or a reaction involving two or more molecules with another compound molecule.

As the compound (a) used in the present invention, any compound can be used as long as it satisfies the above conditions, but it is preferably at least one selected from the following group.

Alkyl halide other than fluorine, aryl halide other than fluorine, aralkyl halide other than fluorine, allyl halide other than fluorine (provided that
In the above alkyl, aryl, aralkyl, and allyl groups, some or all of the hydrogens may be substituted with fluorine), thiol compounds, secondary alcohols, allyl alcohols which may have a substituent, and substituents on the aromatic ring. Benzyl alcohols which may be present, and their esters, ether compounds, sulfide compounds, disulfide compounds, halogen-containing silicon compounds, alkoxysilicon compounds, linear, branched or cyclic acetal compounds N-hydroxyl compounds

Hereinafter, the above compounds (1) to (4) will be described in order.

In the compound of the formula, the above alkyl, aryl, aralkyl,
The allyl group may have some or all of the hydrogen atoms replaced with fluorine atoms, and the above alkyl and aralkyl substituents may be branched.

Specific examples of these compounds are shown below, but are not limited thereto.

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

Compounds Specific examples of these compounds are shown below, but are not limited thereto.

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

Compounds Specific examples of these compounds are shown below, but are not limited thereto.

[0046]

Embedded image

Regarding the Compound (A) As these compounds, compounds having partial structures represented by the following formulas (V) and (U) are preferable.

[0048]

Embedded image

R _c , R _{c ′} , R _{c ″,} which may be the same or different and represent a hydrogen atom, an alkyl group or an aryl group which may have a substituent, and two of them represent It may combine to form a saturated or olefinically unsaturated ring.
L represents a divalent linking group.

In the general formulas (V) and (U), R _c , R
_{When c ′} and R _{c ″} are an aryl group, they generally have 4 to 20 carbon atoms, and include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylmercapto group, and an aminoacyl group. , A carboalkoxy group, a nitro group, a sulfonyl group, a cyano group or a halogen atom. Here, carbon number of 4 to 2
Examples of the zero aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

When R _c , R _{c ′} and R _{c ″} represent an alkyl group, they represent a saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms, and include a halogen atom, Cyano group,
It may be substituted by an ester group, an oxy group, an alkoxy group, an aryloxy group or an aryl group. Here, as a saturated or unsaturated linear or branched or alicyclic alkyl group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group,
t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, isohexyl group, octyl group, isooctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, vinyl group,
Propenyl, butenyl, 2-butenyl, 3-butenyl, isobutenyl, pentenyl, 2-pentenyl, hexenyl, heptenyl, octenyl, cyclopropyl, cyclobutyl, cyclopentyl,
Examples include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopentenyl group, a cyclohexenyl group, and the like.

A saturated or olefinically unsaturated ring formed by bonding any two of R _c , R _{c ′} and R _{c ″} , specifically, a cycloalkane or cycloalkene is usually 3 -8, preferably 5 or 6 ring members.
As the divalent linking group for L, a single bond, an optionally substituted alkylene group, cycloalkylene group, or arylene group, or -O-, -O-CO-Ra1-, -CO
Represents -O-Ra2-, -CO-N (Ra3) -Ra4-. R
a1, Ra2 and Ra4 may be the same or different and may have a single bond, an ether structure, an ester structure, an amide structure, a urethane structure or a ureide structure, and may have a substituent; A cycloalkylene group, an arylene group. Ra3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group which may have a substituent.

In the present invention, in formulas (V) and (U), preferred are those in which R _c , R _{c ′} and R _{c ″} are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. is there.

Specific examples of the compound having a partial structure represented by formulas (V) and (U) are shown below, but it should not be construed that the invention is limited thereto.

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

Compounds Specific examples of these compounds are shown below, but are not limited thereto.

[0061]

Embedded image

As the compound (a), the above-mentioned compound is preferable, and the compound is more preferable.

As these compounds (a), commercially available ones can be appropriately used, and those not commercially available can be easily synthesized by a conventional method. The molecular weight of the compound (a) is 3,000 or less, preferably 2,500 or less, and more preferably 2,000 or less.

The amount of the compound (a) in the resist composition of the present invention is preferably 0.5 to 50% by weight, more preferably 3 to 50% by weight, based on the total weight (solid content) of the composition.
30% by weight.

[II] (b) A compound capable of generating an acid upon irradiation with an energy ray (hereinafter, also referred to as “component (b)”) The above-mentioned energy ray may be a visible light, an ultraviolet ray, an electron beam or an X-ray. Represents As the component (b), any compound can be used as long as it can generate an acid upon irradiation with energy rays.
Compounds represented by (II) are preferred.

[0066] [II-1] in the general formula (I) ~ compounds represented by general formula (II) (I) ~ ( II), a linear R ₁ to R _22,
As the branched alkyl group, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-
Examples thereof include those having 1 to 4 carbon atoms such as -butyl group and t-butyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms which may have a substituent, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. Examples of the linear or branched alkoxy group for R _{1 to} R ₂₃ include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. Such a C1-C4 thing is mentioned. Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. Examples of the halogen atom for R _{1 to} R ₂₂ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The aryl group of R _23, for example, a phenyl group, a tolyl group, methoxyphenyl group, and a good number of 6 to 14 carbon which may have a substituent such as naphthyl.

These substituents are preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom,
A chlorine atom, an iodine atom), an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

Further, among R _{1 to} R ₁₂ and R _{13 to} R ₂₂ , 2
Examples of a ring formed by bonding one or more atoms and containing one or more selected from a single bond, carbon, oxygen, sulfur, and nitrogen include, for example, a furan ring, a dihydrofuran ring, a pyran ring, and a trihydro ring. Examples include a pyran ring, a thiophene ring, a pyrrole ring and the like.

In the general formulas (I) and (II), X ⁻ is a sulfonic acid anion. Examples of the anion of the sulfonic acid include an anion of an alkylsulfonic acid, a benzenesulfonic acid, a naphthalenesulfonic acid, or an anthracenesulfonic acid.

[0070] In the general formula (I) ~ (II), X - as the alkylsulfonic acids having at least one selected from the following group, benzenesulfonic acid, naphthalenesulfonic acid, or an anion of anthracene sulfonic acid preferred . At least one fluorine atom, a linear, branched or cyclic alkyl group substituted with at least one fluorine atom; a linear, branched or cyclic alkoxy group substituted with at least one fluorine atom. Acyl group substituted with a fluorine atom acyloxy group substituted with at least one fluorine atom sulfonyl group substituted with at least one fluorine atom sulfonyloxy group substituted with at least one fluorine atom at least one fluorine Sulfonylamino group substituted with an atom Aryl group substituted with at least one fluorine atom Aralkyl group substituted with at least one fluorine atom and alkoxycarbonyl group substituted with at least one fluorine atom

The linear, branched or cyclic alkyl group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, trifluoromethyl group, pentafluoroethyl group, 2,
Examples thereof include a 2,2-trifluoroethyl group, a heptafluoropropyl group, a heptafluoroisopropyl group, a perfluorobutyl group, a perfluorooctyl group, a perfluorododecyl group and a perfluorocyclohexyl group. Among them, a perfluoroalkyl group having 1 to 4 carbon atoms, all of which is substituted by fluorine, is preferable.

The linear, branched or cyclic alkoxy group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, a trifluoromethoxy group, a pentafluoroethoxy group,
Examples include a heptafluoroisopropyloxy group, a perfluorobutoxy group, a perfluorooctyloxy group, a perfluorododecyloxy group, a perfluorocyclohexyloxy group, and the like. Among them, a perfluoroalkoxy group having 1 to 4 carbon atoms, all of which is substituted by fluorine, is preferable.

The acyl group has 2 to 12 carbon atoms.
Wherein those substituted with 1 to 23 fluorine atoms are preferred. Specific examples include a trifluoroacetyl group, a fluoroacetyl group, a pentafluoropropionyl group, and a pentafluorobenzoyl group.

The acyloxy group has 2 to 2 carbon atoms.
12 which is substituted with 1 to 23 fluorine atoms is preferred. Specific examples include a trifluoroacetoxy group, a fluoroacetoxy group, a pentafluoropropionyloxy group, and a pentafluorobenzoyloxy group.

The sulfonyl group has a carbon number of 1 to 1.
12 which is substituted with 1 to 25 fluorine atoms is preferred. Specific examples include a trifluoromethanesulfonyl group, a pentafluoroethanesulfonyl group, a perfluorobutanesulfonyl group, a perfluorooctanesulfonyl group, a pentafluorobenzenesulfonyl group, and a 4-trifluoromethylbenzenesulfonyl group.

The sulfonyloxy group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specific examples include a trifluoromethanesulfonyloxy group, a perfluorobutanesulfonyloxy group, and a 4-trifluoromethylbenzenesulfonyloxy group.

The sulfonylamino group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specific examples include a trifluoromethanesulfonylamino group, a perfluorobutanesulfonylamino group, a perfluorooctanesulfonylamino group, and a pentafluorobenzenesulfonylamino group.

The aryl group has 6 to 1 carbon atoms.
4, which is substituted with 1 to 9 fluorine atoms is preferable. Specifically, a pentafluorophenyl group, 4
-Trifluoromethylphenyl, heptafluoronaphthyl, nonafluoroanthranyl, 4-fluorophenyl, 2,4-difluorophenyl, and the like.

The aralkyl group has 7 to 7 carbon atoms.
It is preferably 10 and substituted by 1 to 15 fluorine atoms. Specific examples include a pentafluorophenylmethyl group, a pentafluorophenylethyl group, a perfluorobenzyl group, a perfluorophenethyl group, and the like.

The alkoxycarbonyl group preferably has 2 to 13 carbon atoms and is substituted by 1 to 25 fluorine atoms. Specific examples include a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a pentafluorophenoxycarbonyl group, a perfluorobutoxycarbonyl group, and a perfluorooctyloxycarbonyl group.

The most preferred X ⁻ is a fluorine-substituted benzenesulfonic acid anion.

The alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid, or anthracene sulfonic acid having a fluorine-containing substituent further has a linear structure.
A branched or cyclic alkoxy group, an acyl group, an acyloxy group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, an aryl group, an aralkyl group, an alkoxycarbonyl group (the carbon number ranges are the same as those described above),
It may be substituted with a halogen (excluding fluorine), a hydroxyl group, a nitro group, or the like.

Specific examples of the compound represented by formula (I) are shown below.

[0084]

Embedded image

[0085]

Embedded image

Specific examples of the compound represented by formula (II) are shown below.

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

The compounds represented by formulas (I) to (II) may be used alone or in combination of two or more.

The compound of the general formula (I) is obtained by reacting an aryl Grignard reagent such as aryl magnesium bromide with a substituted or unsubstituted phenyl sulfoxide, and subjecting the obtained triaryl sulfonium halide to salt exchange with the corresponding sulfonic acid. , A method of condensing or salt-substituting a substituted or unsubstituted phenyl sulfoxide with a corresponding aromatic compound using an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride, or a method of converting a diaryliodonium salt to a diarylsulfide Can be synthesized by a method such as condensation and salt exchange using a catalyst such as copper acetate. The compound of the formula (II) can be synthesized by reacting an aromatic compound with periodate. The sulfonic acid or sulfonic acid salt used for the salt exchange is obtained by, for example, a method of hydrolyzing a commercially available sulfonic acid chloride, a method of reacting an aromatic compound with chlorosulfonic acid, or a method of reacting an aromatic compound with sulfamic acid. Can be obtained by

Hereinafter, a method for synthesizing specific compounds of the general formulas (I) to (II) will be described below. (Synthesis of Pentafluorobenzenesulfonic Acid Tetramethylammonium Salt) 25 g of pentafluorobenzenesulfonyl chloride was dissolved in 100 ml of methanol under ice cooling.
To this was slowly added 100 g of a 25% aqueous solution of tetramethylammonium hydroxide. After stirring at room temperature for 3 hours, a solution of pentafluorobenzenesulfonic acid tetramethylammonium salt was obtained. This solution was used for salt exchange with sulfonium salt and iodonium salt.

(Synthesis of Triarylsulfonium Pentafluorobensene Sulfonate: Specific Examples (Ia) and (I
Synthesis of a mixture with -1)) Triarylsulfonium chloride 50 g (manufactured by Fluka,
Triphenylsulfonium chloride (50% aqueous solution) was dissolved in 500 ml of water, and an excess amount of a solution of tetramethylammonium pentafluorobenzenesulfonate was added thereto, whereby an oily substance was precipitated. The supernatant was removed by decanting, and the obtained oily substance was washed with water and dried to obtain triarylsulfonium pentafluorobenzensulfonate (mainly containing specific examples (Ia) and (I-1)).

The structural formula of the above (Ia) is shown below.

[0098]

Embedded image

(Synthesis of di (4-t-amylphenyl) iodonium pentafluorobensensulfonate: Synthesis of Specific Example (II-1)) 60 g of t-amylbenzene, 39.5 potassium iodate
g, 81 g of acetic anhydride and 170 ml of dichloromethane were mixed, and 66.8 g of concentrated sulfuric acid was slowly added dropwise thereto under ice-cooling. After stirring for 2 hours under ice cooling, the mixture was stirred at room temperature for 10 hours. To the reaction mixture was added 500 ml of water under ice cooling, and the mixture was extracted with dichloromethane. The organic phase was washed with sodium bicarbonate and water, and concentrated to obtain di (4-t-amylphenyl) iodonium sulfate. This sulfate was added to a solution of an excess amount of tetramethylammonium pentafluorobenzenesulfonate. To this solution was added 500 ml of water, and the mixture was extracted with dichloromethane. The organic phase was washed with a 5% aqueous solution of tetramethylammonium hydroxide and water, and then concentrated to obtain di (4-t-amylphenyl) iodonium pentafluorobenzenesulfonate. Was done.
Other compounds can be synthesized using the same method.

[II-2] Other acid generators that can be used as component (b) In the present invention, component (b) decomposes by irradiation with energy rays as described below to generate an acid. Compounds can also be used. In the present invention, as the component (b), together with the compounds represented by the above general formulas (I) to (II), a compound capable of generating an acid upon being decomposed by irradiation with an energy ray as described below is used. You may use together.

The amount of the acid generator which can be used in combination with the compounds represented by the above general formulas (I) to (II) in the present invention is determined by the molar ratio (in the general formulas (I) to (II)). Compounds / other acid generators), usually from 100/0 to 20 /
80, preferably 100/0 to 40/60, more preferably 100/0 to 50/50. The total content of the component (b) is usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 0.5 to 10% by weight, based on the total solid content of the positive-working chemically amplified resist composition of the present invention. 1 to 7% by weight.

Examples of such an acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, and an electron generator used for a micro resist. Known compounds that generate an acid upon irradiation with X-rays or X-rays and mixtures thereof can be appropriately selected and used.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
Salt, DCNecker etal, Macrom
olecules, 17, 2468 (1984), CSWenetal, Teh, Proc. Conf.
Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.
069,055, phosphonium salts described in 4,069,056 and the like,
JVCrivello etal, Macromorecules, 10 (6), 1307 (197
7), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
No. 4,143, U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,848, Iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17, 73 (1985),
JVCrivelloetal.J.Org.Chem., 43, 3055 (1978), WRWa
tt etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (19
84), JVCrivello etal, Polymer Bull., 14,279 (198
5), JVCrivello etal, Macromorecules, 14 (5), 1141 (19
81), JVCrivello etal, J. Polymer Sci., Polymer Che
m.Ed., 17,2877 (1979), European Patent Nos. 370,693 and 902,
No. 114, No. 233,567, No. 297,443, No. 297,442, U.S. Pat.Nos. 4,933,377, 161,811, No. 410,201, No.
339,049, 4,760,013, 4,734,444, 2,833,8
No. 27, Dokoku Patent Nos. 2,904,626, 3,604,580, 3,6
No. 04,581, etc., sulfonium salt, JVCrivello eta
l, Macromorecules, 10 (6), 1307 (1977), JVCrivello et
al, J. PolymerSci., Polymer Chem. Ed., 17,1047 (1979)
Selenonium salts, CSwen et al, Teh, Proc.Co
Onium salts such as arsonium salts described in nf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), and the like, U.S. Pat.
5, JP-B-46-4605, JP-A-48-36281, JP-A-55-36
32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401
No., JP-A-63-70243, organic halogen compounds described in JP-A-63-298339, K. Meier et al., J. Rad.Curing, 13
(4), 26 (1986), TPGill et al., Inorg.Chem., 19, 3007 (1
980), D. Astruc, Acc.Chem.Res., 19 (12), 377 (1896), JP-A-2-14145, etc., organometallic / organic halides, S. Hayase et al., J. PolymerSci. ., 25, 753 (1987), E. Rei
chmanis etal, J.Pholymer Sci., Polymer Chem.Ed., 23,1
(1985), QQ Zhu et al., J. Photochem., 36, 85, 39, 317 (198
7), B. Amit etal, Tetrahedron Lett., (24) 2205 (1973),
DHR Barton et al., J. Chem Soc., 3571 (1965), PM Coll
ins etal, J. Chem.SoC., Perkin I, 1695 (1975), M. Rudinst
ein etal, Tetra hedron Lett., (17), 1445 (1975), JWW
alker etal J. Am. Chem. Soc., 110, 7170 (1988), SCBusma
n etal, J. Imaging Technol., 11 (4), 191 (1985), HMHoul
ihanetal, Macormolecules, 21, 2001 (1988), PMCollins
etal, J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase
etal, Macromolecules, 18, 1799 (1985), E. Reich maniseta
l, J.Electrochem.Soc., Solid State Sci.Technol., 130
(6), FMHouli han etal, Macromolcules, 21, 2001 (198
8), European Patent Nos. 0290,750, 046,083, 156,535
No. 271,851, No. 0,388,343, U.S. Pat.No. 3,901,7
No. 10, 4,181,531, JP-A-60-198538, JP-A-53-1
Photoacid generator having an o-nitrobenzyl-type protecting group described in No. 33022, M. TUNOOKA et al., Polymer Preprints Ja
pan, 35 (8), G. Berner et al., J. Rad. Curing, 13 (4), WJMij
s etal, Coating Technol., 55 (697), 45 (1983), Akzo, H.Ad
achi etal, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115
Nos. 0101,122; U.S. Pat.Nos. 618,564; 4,371,605
No. 4,431,774, JP-A-64-18143, JP-A-2-2-2457
No. 56, Japanese Patent Application No. 3-140109, etc., compounds generating sulfonic acid represented by iminosulfonate and the like, and disulfone compounds described in JP-A-61-166544 and the like can be mentioned.

Compounds in which a group or a compound which generates an acid upon irradiation with these energy rays is introduced into the main chain or side chain of the polymer, for example, MEWoodhouse eta
l, J. Am. Chem. Soc., 104, 5586 (1982), SPPappas etal,
J. Imaging Sci., 30 (5), 218 (1986), S. Kondo et al., Makro
mol.Chem., Rapid Commun., 9,625 (1988) ,. Yamadaetal, M
akromol.Chem., 152, 153, 163 (1972), JVCrivello eta
1, J. Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.No. 3,849,137, Dokoku Patent 3914407, JP-A-63
-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-1538
No. 53, JP-A-63-146029 and the like can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
The compounds capable of generating an acid described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the above compounds which can be used together and which generate an acid by being decomposed by irradiation with an energy ray, those which are particularly effectively used will be described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PAG)
An S-triazine derivative represented by 2).

[0107]

Embedded image

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

(2) A sulfonium salt represented by the general formula (PAG4).

[0113]

Embedded image

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents include an aryl group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group,
A carboxyl group, a hydroxy group and a halogen atom, and an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group.

[0115] Z ^- represents a counter anion, for example BF ₄ ^-,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, these may be mentioned sulfonic acid group-containing dyes It is not limited.

Two of R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ may be bonded to each other via a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

The above onium salt represented by the general formula (PAG4) is known, for example, JWKnapczyk et al., J. Am.
m. Soc., 91, 145 (1969), ALMaycok et al., J. Org. Chem.,
35, 2532, (1970), E. Goethas et al., Bull. Soc. Chem. Bel.
g., 73, 546, (1964), HM Leicester, J. Ame. Chem. Soc., 5
1,3587 (1929), JVCrivello etal, J. Polym. Chem. Ed., 1
8,2677 (1980); U.S. Pat.Nos. 2,807,648 and 4,247,47
No. 3, JP-A-53-101,331 and the like.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0128]

Embedded image

In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶ Is replaced or
It represents an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

In the present invention, the component (b) is a compound which generates an acid upon irradiation with energy rays.
Any of them can be used, but the reduction potential is-
It is preferably 0.5 V (vs SCE) or more.
For the evaluation method of the reduction potential, see the electrochemical measurement method (above)
And (below) (Gihodo Shuppan, 1984).

In the present invention, (d) a resin having a group which can be decomposed by an acid and having a solubility in an alkali developing solution increased by the action of an acid (hereinafter, also referred to as “component (d)”); e) at least a low-molecular-weight dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter, also referred to as “component (e)”) having a group decomposable by an acid and having increased solubility in an alkali developer due to the action of an acid. It is preferable to contain either one.

[III] (e) Resin having an acid-decomposable group and having increased solubility in an alkali developing solution by the action of an acid Component (e) used in the positive chemically amplified resist composition of the present invention Is a resin having an acid-decomposable group in the main chain or side chain of the resin, or in both the main chain and the side chain. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable. Preferred group capable of decomposing by an acid is, -COOA ^0, a -O-B ⁰ group, further examples of the group containing these, -R ⁰ -COOA ^0, or -A _r -O-
Groups represented by B ⁰ the like. Here, A ⁰ is -C (R
⁰¹ ) ( ^R02 ) ( ^R03 ), -Si ( ^R01 ) ( ^R02 )
Shows the (R ^{0 3)} or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰ represents A ⁰ or a —CO—O—A ⁰ group (R ⁰ , R ^{01 to} R ⁰⁶ , and Ar have the same meanings as described below).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ester. And tertiary alkyl carbonate groups. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group.

[0139] Next, as the matrix resin in the case where the group capable of decomposing by an acid is bonded as a side chain, -OH or -COOH in the side chain, preferably -R ⁰ -COOH or -A _r -OH group It is an alkali-soluble resin having. For example, an alkali-soluble resin described below can be used.

The alkali dissolution rate of these alkali-soluble resins was measured (at 23 ° C.) using 0.261N tetramethylammonium hydroxide (TMAH), and was 170
A / sec or more is preferable. Particularly preferably 330A
/ Sec or more (A is angstroms). From such a viewpoint, a particularly preferred alkali-soluble resin is
o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkyl And styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers and hydrogenated novolak resins.

The component (e) used in the present invention is described in European Patent No. 248553, JP-A-2-25850 and 3-2.
No. 23860, 4-251259, etc., an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer to which an acid-decomposable group is bonded is used. It can be obtained by copolymerization with various monomers.

Specific examples of the component (e) used in the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

[0147]

[Of 60]

[0148]

Embedded image

[0149]

Embedded image

The content of acid-decomposable groups is determined by the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S). B /
It is represented by (B + S). The content is preferably 0.01 to
0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40. B / (B + S)>
A value of 0.7 is not preferred because it causes film shrinkage after PEB, poor adhesion to the substrate, and scum. On the other hand, B / (B + S) <
A value of 0.01 is not preferable because standing waves may be remarkably left on the pattern side wall.

The weight average molecular weight (Mw) of the component (e) is
It is preferably in the range of 2,000 to 200,000. If the molecular weight is less than 2,000, the film loss is large due to the development of the unexposed portion. If the molecular weight exceeds 200,000, the dissolution rate of the alkali-soluble resin itself in alkali becomes slow and the sensitivity is lowered. More preferably, 5,000 to 100,0
00, more preferably from 8,000 to 50,
000. In addition, molecular weight distribution (Mw / Mn)
Is preferably 1.0 to 4.0, more preferably 1.0 to 4.0.
-2.0, particularly preferably 1.0-1.6, and the smaller the degree of dispersion, the better the heat resistance and image forming properties (pattern profile, etc.). Here, the weight average molecular weight is
It is defined as the value in terms of polystyrene of gel permeation chromatography. The component (e) is 2
You may use it in combination of types or more.

[IV] (f) Low-molecular acid-decomposable dissolution inhibiting compound ("component (f)") In the present invention, the component (f) may be used. The component (f) has a group that can be decomposed by an acid, and the solubility in an alkali developer increases by the action of an acid.
It is a low molecular weight dissolution inhibiting compound of 0 or less. The preferred component (f) to be blended in the composition of the present invention has at least two groups capable of being decomposed by an acid in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, It is a compound that passes through at least eight bonding atoms excluding a sex group. A more preferred component (f) has at least two groups capable of being decomposed by an acid in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, at least a bonding atom excluding the acid-decomposable group. A compound via at least 10, preferably at least 11, more preferably at least 12, or at least three acid-decomposable groups, and at the position where the distance between the acid-decomposable groups is the longest, an acid-decomposable group Is a compound having at least 9, preferably at least 10, and more preferably at least 11 bonding atoms excluding. The preferred upper limit of the number of the bonding atoms is 50, more preferably 30. When the acid-decomposable dissolution-inhibiting compound as the component (f) has three or more, preferably four or more acid-decomposable groups, the acid-decomposable group also has two acid-decomposable groups. When they are separated from each other by a certain distance or more, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved. The distance between the acid-decomposable groups is represented by the number of via bond atoms excluding the acid-decomposable groups. For example, the following compound (1),
In the case of (2), the distance between the acid-decomposable groups is 4
And in compound (3), 12 bonding atoms.

[0153]

Embedded image

The acid-decomposable dissolution-inhibiting compound as the component (f) may have a plurality of acid-decomposable groups on one benzene ring, but preferably has one on one benzene ring. It is a compound composed of a skeleton having one acid-decomposable group. Further, the acid-decomposable dissolution-inhibiting compound of the present invention has a molecular weight of 3,000 or less, preferably 300 to 3.0.
00, more preferably 500 to 2,500.

In a preferred embodiment of the present invention, groups decomposable by an acid, that is, -COO-A ⁰ , -OB ^0.
The group containing a group, -R ⁰ -COO-A ^0, or -Ar
Include groups represented by -O-B ^0. Where A ⁰ is −
C ( ^R01 ) ( ^R02 ) ( ^R03 ), -Si ( ^R01 ) ( ^R02 )
Shows the (R ^{0 3)} or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰ represents A ⁰ or a —CO—OA ⁰ group.
R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group;
⁰⁶ represents an alkyl group or an aryl group. Where R ⁰¹
At least two of to R ⁰³ is a group other than a hydrogen atom,
Further, two groups out of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ may combine to form a ring. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

Here, the alkyl group is preferably a group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred.

As the substituent, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above-mentioned alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group Alkoxy groups such as groups, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, Aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, the above alkenyl group, vinyloxy group, propenyloxy group, allyloxy group, butenyloxy group Alkenyloxy groups such as Serial aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

Preferably, a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group,
And a tertiary alkyl ester group and a tertiary alkyl carbonate group. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

As the component (f), preferably, JP-A-1-289946, JP-A-1-289947, JP-A-2-2560, JP-A-3-128959, JP-A-3-158855, and JP-A-3-158855 3-179353, JP-A-3-191351, JP-A-3-200251, JP-A-3-200252, JP-A-3-200253,
JP-A-3-200254, JP-A-3-200255
JP-A-3-259149, JP-A-3-27995
8, JP-A-3-279959, JP-A-4-1650
No., JP-A-4-1651, JP-A-4-11260,
JP-A-4-12356, JP-A-4-12357, JP-A-3-33229, JP-A-3-230790, JP-A-3-320438, JP-A-4-25157, JP-A-4 -52732, Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107885,
A group in which part or all of the phenolic OH group of the polyhydroxy compound described in the specification of Japanese Patent Application Nos. 4-107889 and 4-152195 is -R ^0-
Linked by COO-A ⁰ or B ⁰ groups include protected compound.

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

More specifically, general formulas [I] to [XV]
The compound represented by I] is mentioned.

[0162]

Embedded image

[0163]

Embedded image

[0164]

Embedded image

[0165]

Embedded image

Here, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ and R ¹³⁰ may be the same or different, and represent a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ ) (R
⁰²⁾ (R ⁰³⁾ or ^{-CO-O-C (R 01} ) (R 0 2) (R
⁰³ ) provided that the definitions of R ⁰ , R ⁰¹ , R ⁰² and R ⁰³ are the same as described above.

R ¹⁰⁰ : -CO-, -COO-, -NHC
ONH-, -NHCOO-, -O-, -S-, -SO
-, -SO _2- , -SO _3- , or

[0168]

Embedded image

[0169] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ^{15 3} or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,, R ^99, R ¹⁰³ ~ R ¹⁰⁷ , R ¹⁰⁹ , R ^{111
~R 118, R 121 ~R 123,} R 128 ~R 129, R 131 ~
R ¹³⁴ , R ^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group; A halogen atom, a nitro group, a carboxyl group, a cyano group, or —N (R ¹⁵⁵ ) (R ¹⁵⁶ ) (where R ¹⁵⁵ and R ^{156 are} H,
An alkyl group or an aryl group) ^R110 : a single bond, an alkylene group, or

[0170]

Embedded image

R ¹⁵⁷ and R ¹⁵⁹ may be the same or different, and represent a single bond, an alkylene group, —O—, —S—, —CO
— Or carboxyl group, R ¹⁵⁸ : hydrogen atom, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, nitro group, hydroxyl group, cyano group, or carboxyl group, provided that the hydroxyl group is an acid-decomposable group (for example, t-butoxycarbonylmethyl group, tetrahydropyranyl group, 1-ethoxy-1-ethyl group,
(1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ¹²⁰ may be the same or different and are each a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group means an alkyl group having 1 to 4 carbon atoms. R ^{124 to} R ¹²⁷ may be the same or different and may be a hydrogen atom or an alkyl group; R ^{135 to} R ¹³⁷ may be the same or different and a hydrogen atom;
An alkyl group, an alkoxy group, an acyl group, or an acyloxy group, R ¹⁴² : a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ )
( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 ) ( ^R02 )
(R ⁰³ ), or

[0173]

Embedded image

R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
Or an aryl group, R ^{146 to} R ¹⁴⁹ : may be the same or different, and may be hydrogen, hydroxyl, halogen, nitro, cyano, carbonyl, alkyl, alkoxy, alkoxycarbonyl, aralkyl, aralkyloxy A group, an acyl group, an acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that the four substituents having the same symbols do not have to be the same group. : —CO— or —SO ₂ —, Z, B: single bond or —O—, A: methylene group, lower alkyl-substituted methylene group, halomethylene group, or haloalkyl group; E: single bond or oxymethylene group , A to z, a1 to y1: When plural, the groups in () may be the same or different; a to q, s, t, v, g1 to i1, k1 to m1 , o1, q1, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1 to f1, p1, r1, t1, v1 to x1: 0 or 1
An integer of 4, j1, n1, z1, a2, b2, c2, d2: an integer of 0 or 1 to 3, at least one of z1, a2, c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s), (w + x + y), (c1 + d1), (g1 +
h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2, (j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1),
(t1 + v1), (x1 + w1) ≦ 4, provided that (w +
z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q
+ t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1), (s1 + u1)
≦ 5.

[0175]

Embedded image

[0176]

Embedded image

[0177]

Embedded image

[0178]

Embedded image

Specific examples of preferred compound skeletons are shown below.

[0180]

[Of 75]

[0181]

Embedded image

[0182]

Embedded image

[0183]

Embedded image

[0184]

Embedded image

[0185]

Embedded image

[0186]

Embedded image

[0187]

Embedded image

[0188]

Embedded image

[0189]

Embedded image

[0190]

Embedded image

[0191]

Embedded image

[0192]

Embedded image

R in the compounds (1) to (44) is a hydrogen atom,

[0194]

Embedded image

Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
May not be the same group.

[V] In the present invention, as other components,
(G) A resin that is insoluble in water and soluble in an alkali developer (hereinafter, also referred to as “(g) component” or “(g) alkali-soluble resin”) can be used. In the positive chemically amplified resist composition of the present invention, as the component (g), a resin that is insoluble in water and soluble in an aqueous alkaline solution can be used. When the component (g) is used, it is not always necessary to incorporate a resin having a group that is decomposed by the action of the acid as the component (g) and increases the solubility in an alkali developer. Of course, this does not exclude the combination with the component (g).

Examples of the alkali-soluble resin (g) used in the present invention include novolak resins, hydrogenated novolak resins, acetone-pyrogallol resins, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogen Polyhydroxystyrene,
Halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, part of O- to hydroxyl group of polyhydroxystyrene
Alkyl compounds (for example, 5 to 30 mol% of O-methyl compound, O- (1-methoxy) ethyl compound, O- (1-ethoxy) ethyl compound, O-2-tetrahydropyranyl compound, O- (t- Butoxycarbonyl) methylated product) or O-acylated product (for example, 5 to 30 mol% o-
Acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-
Examples thereof include, but are not limited to, hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and its derivative, and polyvinyl alcohol derivative.

Particularly preferred (g) alkali-soluble resins are novolak resins and o-polyhydroxystyrene,
Polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially O-alkylated or O-acylated polyhydroxystyrene, styrene-hydroxystyrene copolymer, α-methyl It is a styrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, Alkoxyphenols such as -methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropyl Fenault Bis-alkylphenols etc., m
Hydroxychloro compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or in combination of two or more, but are not limited thereto. It is not something to be done.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-
Phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o -Methylbenzaldehyde, m-methylbenzaldehyde,
p-Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde, and their acetal compounds, such as chloroacetaldehyde diethyl acetal, among which formaldehyde is used Is preferred. These aldehydes are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The novolak resin thus obtained preferably has a weight average molecular weight in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000-20,
000. In addition, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 5,000.
~ 200000, more preferably 5000-10000
0. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. These (g) alkali-soluble resins in the present invention may be used in combination of two or more.

Here, examples of the constitution of the composition of the present invention are illustrated below. However, the content of the present invention is not limited to these. 1) The component (a), the component (b), and the component (c)
And a positive chemically amplified resist composition comprising the above component (e). 2) A positive chemically amplified resist composition comprising the above components (a), (b), (c), (f) and (g). 3) A positive chemically amplified resist composition comprising the above components (a), (b), (c), (e) and (f).

In each of the above constitution examples, the amount of the component (e) of 1), the component (g) of 2) and the component (e) of 3) used in the composition are each based on the solid content of the total composition. 40 ~
It is preferably 99% by weight, more preferably 50 to 95% by weight.

The amount of the component (f) used in the composition is 3 to 4 with respect to the solid content of the whole composition in any of the above constitution examples.
Preferably 5% by weight, more preferably 5 to 30% by weight,
More preferably, it is 10 to 30% by weight.

[VI] (c) Organic basic compound The organic basic compound (c) used in the present invention is a compound which is more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. As a preferred chemical environment,
The following formulas (A) to (E) may be mentioned.

[0206]

Embedded image

Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol,
Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted Or, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group.

As particularly preferred compounds, guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, , 4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine,
-(Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, -Aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2
-Aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-amino Ethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole,
5-amino-3-methyl-1-p-tolylpyrazole,
Pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6
-Dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, diazabicyclononene, diazabicycloundecene, and the like, but are not limited thereto. is not.

These (c) organic basic compounds can be used alone or in combination of two or more.
The amount of the organic basic compound to be used is generally 0.01 to the compound (a) of the present invention which generates an acid upon irradiation with radiation.
-10 mol%, preferably 0.1-5 mol%.
If it is less than 0.01 mol%, the effect of the addition cannot be obtained.
On the other hand, if it exceeds 10 mol%, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

[VII] (d) Fluorine and / or silicon surfactant In the present invention, (d) a fluorine and / or silicon surfactant can be used. For example, F Top E
F301, EF303 (manufactured by Shin-Akita Chemical Co., Ltd.), Florado FC430, 431 (manufactured by Sumitomo 3M Limited),
Mega Fuck F171, F173, F176, F18
9, R08 (Dainippon Ink Co., Ltd.), Surflon S-
382, SC-101, 102, 103, 104, 10
5, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366
(Manufactured by Troy Chemical Co., Ltd.) or a silicon-based surfactant. Also,
Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

A surfactant other than a fluorine-based and / or silicon-based surfactant can be used in combination. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether and the like Sorbitan such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate; acrylic acid or methacrylic acid (Co) polymerized polyflow no. 75, no. 9
5 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

The amount of these surfactants is usually 2% by weight or less, preferably 1% by weight or less, based on the solid content of the whole composition in the composition of the present invention. These surfactants may be added alone or in combination of two or more.

[VIII] Other components used in the present invention The positive-working chemically amplified resist composition of the present invention may further contain, if necessary, a dye, a pigment, a plasticizer, a photosensitizer and a developer. A compound having two or more phenolic OH groups for promoting the property can be contained.

The compound having two or more phenolic OH groups that can be used in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. Further, it is necessary to have at least two phenolic hydroxyl groups in the molecule. If the number exceeds 10, the effect of improving the development latitude is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The preferred addition amount of this phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin (g). 50% by weight
If the addition amount exceeds the above range, the development residue becomes worse and a new defect that the pattern is deformed at the time of development occurs, which is not preferable.

Such phenol compounds having a molecular weight of 1,000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized at Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

Resorcin, phloroglucin, 2,3,4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside,
4,2 ', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2',
4,4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2', 4,4'-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl)-
1-ethyl-4-isopropylbenzene, 1,2,2-
Tris (hydroxyphenyl) propane, 1,1,2-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α , Α ', α'-tetrakis (4-hydroxyphenyl)]-xylene.

The composition of the present invention is dissolved in a solvent capable of dissolving the above-mentioned components, and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, and the like are preferable, and these solvents can be used alone or in combination. it can. In the present invention, as a coating solvent, propylene glycol monomethyl ether acetate is particularly preferred, whereby the in-plane uniformity becomes excellent.

In pursuit of further advances in semiconductors, in addition to the essential performance of the resist such as high resolution, sensitivity, applicability, minimum application amount, adhesion to the substrate, heat resistance, preservation of the composition From various viewpoints such as stability, a high-performance composition is required. Recently, there has been a tendency to create devices using large diameter wafers in order to increase the absolute amount of chips that can be obtained. However, if the coating is applied to a large diameter, there is a concern that the coating properties, particularly the in-plane film thickness uniformity, may be reduced. Therefore, it is required to improve the film thickness in-plane uniformity for a large diameter wafer. As a method for confirming the uniformity, the film thickness is measured at many points in the wafer, the standard deviation of each measured value is obtained, and the uniformity can be confirmed by a value three times the standard deviation. It can be said that the smaller this value is, the higher the in-plane uniformity is. As the value, a value three times the standard deviation is preferably 100 or less, more preferably 50 or less.
CD linearity is regarded as the most important factor in the production of photolithography masks, and there is a demand for improved uniformity of the film thickness within a blank.

[0220] The resist composition of the present invention can be filtered after being dissolved in a solvent. The filter used for that purpose is selected from those used in the resist field, and specifically, the material of the filter is polyethylene,
Those containing nylon or polysulfone are used. More specifically, micro guard manufactured by Millipore,
Microguard Plus, Microguard Minichem-
D, Microgard Minichem-D PR, Millipore Obturizer DEV / DEV-C, Millipore Obturizer 16/14, Ultipore N66 manufactured by Pall, Posidyne, Nylon Falcon and the like. The pore diameter of the filter can be the one confirmed by the following method. In other words, PSL standard particles (polystyrene latex beads, particle size 0.100 μm) in ultrapure water
Is dispersed and continuously flowed at a constant flow rate to the primary side of the filter by a tube pump, and the challenge concentration is measured by a particle counter. Those that can capture 90% or more can be used as a 0.1 μm pore size filter.

The positive chemically amplified resist composition of the present invention is applied to a substrate (eg:
After coating on a silicon / silicon dioxide coating) or a substrate for photolithography mask manufacturing (eg, glass / Cr coating) by an appropriate coating method such as a spinner or a coater,
By exposing through a predetermined mask, baking and developing, a good resist pattern can be obtained.

Examples of the developing solution of the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and ethylamine and n-propylamine. Monoamines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium An alkaline aqueous solution such as a quaternary ammonium salt such as hydroxide, or a cyclic amine such as pyrrole or piperidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0223]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto. [Synthesis Example 1: Synthesis of poly (p-hydroxystyrene / styrene) copolymer] 35.25 of a p-tert-butoxystyrene monomer dehydrated and purified by distillation according to a conventional method.
g (0.2 mol) and 5.21 g of styrene monomer
(0.05 mol) was dissolved in 100 ml of tetrahydrofuran. Under a nitrogen stream and stirring, at 80 ° C., 0.033 g of azobisisobutyronitrile (AIBN) was added three times every 2.5 hours, and finally, stirring was continued for another 5 hours to carry out a polymerization reaction. . The reaction solution was hexane 1200
Then, white resin was precipitated. After drying the obtained resin, it was dissolved in 150 ml of tetrahydrofuran.
4N hydrochloric acid was added thereto, and the mixture was hydrolyzed by heating under reflux for 6 hours, and then reprecipitated in 5 L of ultrapure water. The resin was separated by filtration, washed with water and dried. Further, it was dissolved in 200 ml of tetrahydrofuran, and dropped and reprecipitated in 5 L of ultrapure water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / styrene) copolymer.

[Synthesis Example 2: Synthesis of Resin Example (c-21)]
32.4 g (0.2 mol) of p-acetoxystyrene and 7.01 g (0.07 mol) of t-butyl methacrylate were dissolved in 120 ml of butyl acetate, and the mixture was dissolved under a nitrogen stream and stirring.
Azobisisobutyronitrile (AIBN) at 80 ° C
0.033 g was added three times every 2.5 hours, and finally, stirring was continued for another 5 hours to carry out a polymerization reaction.
The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. After drying the obtained resin, methanol 200
Dissolved in ml. 7.7 g of sodium hydroxide
An aqueous solution of (0.19 mol) / water (50 ml) was added, and the mixture was heated at reflux for 1 hour to hydrolyze. Thereafter, 200 ml of water was added for dilution, and neutralized with hydrochloric acid to precipitate a white resin. This resin was separated by filtration, washed with water and dried.
Further, it was dissolved in 200 ml of tetrahydrofuran, and dropped and reprecipitated in 5 L of ultrapure water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / t-butyl methacrylate) copolymer.

[Synthesis 3: Synthesis of resin example (c-3)] Poly (p-hydroxystyrene) (VP-Nippon Soda Co., Ltd.)
8000) was dissolved in 50 ml of pyridine, and 3.63 g of di-tert-butyl dicarbonate was added dropwise thereto at room temperature with stirring. After stirring at room temperature for 3 hours, 1 L of ion exchanged water /
The solution was added dropwise to a solution of 20 g of concentrated hydrochloric acid. The precipitated powder is filtered,
After washing with water and drying, a resin example (c-3) was obtained.

[Synthesis 4: Synthesis of Resin Example (c-33)] p
-83.1 g (0.5 mol) of cyclohexylphenol
Was dissolved in 300 ml of toluene, then 150 g of 2-chloroethyl vinyl ether, 25 g of sodium hydroxide,
5 g of tetrabutylammonium bromide and 60 g of triethylamine were added and reacted at 120 ° C. for 5 hours. The reaction solution was washed with water, excess chloroethyl vinyl ether and toluene were distilled off, and the obtained oil was purified by distillation under reduced pressure.
4-Cyclohexylphenoxyethyl vinyl ether was obtained. 20 g of poly (p-hydroxystyrene) (VP-8000 manufactured by Nippon Soda Co., Ltd.) and 6.5 g of 4-cyclohexylphenoxyethyl vinyl ether were added to THF80.
dissolved in 0.01 ml of p-toluenesulfonic acid.
g was added and reacted at room temperature for 18 hours. The reaction solution was added dropwise to 5 L of distilled water with vigorous stirring, and the precipitated powder was filtered and dried to obtain a resin example (c-33).

Resin Examples (c-4), (c-28), (c-
30) was also synthesized by the same method using the corresponding trunk polymer and vinyl ether.

Instead of poly (P-hydroxystyrene) (VP-8000 manufactured by Nippon Soda Co., Ltd.), poly (P-hydroxystyrene) (VP-500 manufactured by Nippon Soda Co., Ltd.) was used.
(C-3) ′, (c-3)
3) ', (c-4)', (c-28) ', (c-3)
0) '. Further, the amount of the initiator is controlled to reduce the molecular weight to 6%.
Polymers (poly (P-hydroxystyrene / styrene) copolymers (2) and (c-21) ′) having about a percentage were obtained.

(Synthesis Example 1 of Dissolution Inhibitor Compound: Synthesis of Compound Example 16) 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis ( 4 "
-Hydroxyphenyl) ethyl] benzene 42.4 g
(0.10 mol) in N, N-dimethylacetamide 30
09.5 ml, and potassium carbonate 49.5 g (0.
35 mol), and 84.8 g of cumyl bromoacetate
(0.33 mol) was added. Then, at 120 ° C, 7
Stirred for hours. The reaction mixture was poured into 2 l of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. Concentrated ethyl acetate extract, purified, (all _{R -CH 2 COOC (CH 3)} 2 C 6 H 5 group) Compound Example 16 was obtained 70 g.

(Synthesis Example 2 of Dissolution Inhibitor Compound: Synthesis of Compound 41) 44 g of 1,3,3,5-tetrakis- (4-hydroxyphenyl) pentane was dissolved in 250 ml of N, N-dimethylacetamide. 70.7 g of potassium carbonate and then 90.3 g of t-butyl bromoacetate were added thereto, followed by stirring at 120 ° C. for 7 hours. The reaction mixture was poured into 2 l of ion-exchanged water, and the obtained viscous material was washed with water. This was purified by column chromatography to give Compound Example 4.
1 (all R is _{-CH 2 COOC 4 H 9 (t} )) is 87
g were obtained.

(Synthesis Example 3 of Dissolution Inhibitor Compound: Synthesis of Compound Example 43) α, α, α ′, α ′, α ″, α ″,-hexakis (4-hydroxyphenyl) -1,3,5 20 g of triethylbenzene in 400 ml of diethyl ether
Was dissolved. Under a nitrogen atmosphere, 42.4 g of 3,4-dihydro-2H-pyran and a catalytic amount of hydrochloric acid were added to this solution,
Refluxed for 24 hours. After the completion of the reaction, a small amount of sodium hydroxide was added, followed by filtration. The filtrate was concentrated and purified by column chromatography to obtain 55.3 g of Compound Example 43 (R is all THP groups).

(Synthesis Example 4 of Dissolution Inhibitor Compound: Synthesis of Compound Example 43-2) α, α, α ′, α ′, α ″, α ″,
-Hexakis (4-hydroxyphenyl) -1,3,5
-Dissolved in 20 g of triethylbenzene and 200 ml of N, N-dimethylacetamide.
8.2 g and then 36.0 g of butyl bromoacetate were added and 1
The mixture was stirred at 20 ° C. for 7 hours. The reaction product was poured into 2 liters of ion-exchanged water, and the obtained viscous material was washed with water. When this was purified by column chromatography, the above compound example 43-2 (R was all -CH ₂ COOC ₄ H ₉ (t)) was 3
7 g were obtained.

[(A) Synthesis Example of Compound that Generates Radical (A) Directly or Indirectly by Irradiation with Energy Beam]

(Synthesis Example-1) 2-bromomethyl-1,3
-Dioxolane and terephthalic acid were equimolarly mixed with potassium carbonate in an amount of 5 times and reacted at 60 ° C. Water was added to the mixture, which was extracted with ethyl acetate. After washing with water, drying was performed to obtain (b-6) as a white solid. Other compounds (b-
7) to (b-8) were obtained by the same operation. Also, (b
-4), (b-9) to (b-40) used commercially available compounds.

Compounds (b-4), (b-6) to (b-4)
0) is as follows.

[0236]

Embedded image

[0237]

Embedded image

[0238]

Embedded image

[0239]

Embedded image

Examples [Examples and Comparative Examples] (1) Coating of resist The components shown in Tables 1 to 7 below were dissolved in 8.2 g of propylene glycol monomethyl ether acetate, and this was dissolved in 0.1 μm Teflon (registered). (Trademark) filter to prepare a resist solution. The composition of Example 35 used 8.2 g of ethyl lactate as a solvent. Each sample solution was applied on a silicon wafer using a spin coater, and dried on a vacuum adsorption type hot plate at 110 ° C. for 90 seconds to obtain a 0.5 μm-thick resist film A. Further, each sample solution was applied on a silicon wafer using a spin coater, and dried on a vacuum suction type hot plate at 110 ° C. for 90 seconds to obtain a resist film B having a thickness of 0.4 μm.

(2) Preparation of resist pattern An electron beam lithography system (pressing voltage 5
(0 KV). After the irradiation, each was heated on a vacuum suction hot plate (110 ° C. for 60 seconds (A), 1
It was heated at 10 ° C. for 60 seconds (B), immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. Obtained contact hole pattern (resist film A
) And the cross-sectional shape of the line and space pattern (using the resist film B) were observed with a scanning electron microscope.

(3) Evaluation of sensitivity and resolving power The limiting resolving power (minimum diameter of the hole) in the contact hole pattern was defined as the resolving power, and the minimum irradiation dose capable of resolving the limiting resolving power was defined as the sensitivity. Further, the sensitivity was defined as the irradiation amount that resolved 0.2 μm into the design dimensions in a line-and-space pattern at a ratio of 1: 1 and the minimum size that could be resolved at the irradiation amount was defined as the resolution.

(4) Evaluation of PCD The resist film obtained by the method (1) was allowed to stand in an electron beam lithography apparatus for 150 minutes under a high vacuum, and then a resist pattern was formed by the method (2). The minimum contact hole size (diameter) or line and space that can be resolved with the same irradiation amount as the sensitivity obtained by the method (3) (in this case, irradiation immediately after forming the resist film, without leaving it in a high vacuum for 150 minutes, but immediately irradiating). Ask for. The closer this size is to the limit resolution obtained in (3), the more PC
D stability is good.

(5) Evaluation of PED A resist pattern was formed in the same manner as in (2) except that a step of standing for 150 minutes in a high vacuum in an electron beam lithography apparatus after irradiation was added. The minimum contact hole size (diameter) or resolution that can be resolved with the same irradiation dose as the sensitivity obtained by the method (3) (in this case, there is no step of leaving under high vacuum for 150 minutes after irradiation, and heating is performed immediately). Ask for line and space. The closer the size and the critical resolution obtained in (3) are, the more PE
D stability is good.

[0245]

[Table 1]

[0246]

[Table 2]

[0247]

[Table 3]

[0248]

[Table 4]

[0249]

[Table 5]

[0250]

[Table 6]

[0251]

[Table 7]

The acid generator PAG-1 is as follows.

[0253]

Embedded image

The composition, physical properties and the like of the binder resin used are as follows. (C-3): p-humanoxystyrene / pt-butoxycarboxystyrene copolymer (molar ratio: 80/2)
0), weight average molecular weight (Mw) 13000, molecular weight distribution (Mw / Mn) 1.4 (c-3) ′: Mw 8000

(C-4): p-hydroxystyrene / p
-(1-ethoxyethoxy) styrene copolymer (molar ratio: 70/30), Mw 12000, molecular weight distribution (Mw
/ Mn) 1.3 (c-4) ': Mw 7000

(C-21): p-hydroxystyrene /
t-butyl methacrylate copolymer (molar ratio: 70/3)
0), Mw 16000, molecular weight distribution (Mw / Mn)
0 (c-21) ': Mw 9500

(C-22): p-hydroxystyrene /
p- (1-t-butoxyethoxy) styrene copolymer (molar ratio: 85/15), Mw 12000, molecular weight distribution (Mw / Mn) 1.1 (c-22) ': Mw 7000

(C-28): p-hydroxystyrene /
p- (1-phenethyloxyethoxy) styrene copolymer (molar ratio: 85/15), Mw 12000, molecular weight distribution (Mw / Mn) 1.2 (c-28) ': Mw 7000

(C-30): p-hydroxystyrene /
p- (1-phenoxyethoxyethoxy) styrene copolymer (molar ratio: 85/15), Mw 13,000, molecular weight distribution (Mw / Mn) 1.2 (c-30) ': Mw 8000

(C-33): p-hydroxystyrene /
p- (1-p-cyclohexylphenoxyethoxy) styrene copolymer (molar ratio: 85/15), Mw 1300
0, molecular weight distribution (Mw / Mn) 1.2 (c-33) ′: Mw 8000

(PHS-1): Poly (P-hydroxystyrene) (Nippon Soda Co., Ltd., trade name VP-8000) (PHS-2): Poly (P-hydroxystyrene) (Nippon Soda Co., Ltd.) (Trade name: VP-5000) (PHS-3): Poly (P-hydroxystyrene) (trade name: H-80A, manufactured by Toho Chemical Co., Ltd.) (PHS-4): Poly (P-hydroxystyrene) (Toho Chemical) (Trade name: H-60A)

(PHS / St: synthesized in Synthesis Example 1): p-hydroxystyrene / styrene (molar ratio: 8
0/20), Mw 26000, molecular weight distribution (Mw / M
n) 1.9 (PHS / St2): Mw 15600

The following are the organic basic compounds. B-1: 2,4,5-triphenylimidazole B-2: 1,5-diazabicyclo [4.3.0] nona
5-ene B-3: 4-dimethylaminopyridine B-4: 1,8-diazabicyclo [5.4.0] undec-7-ene B-5: N-cyclohexyl-N'-morpholinoethylthiourea

The surfactant is as follows. W-1: Troysol S-366 (Troy Chemical Co., Ltd.)
W-2: Megafac F176 (Dainippon Ink Co., Ltd.)
W-3: Megafac R08 (Dai Nippon Ink Co., Ltd.) W-4: Polysiloxane polymer KP-341 (Shin-Etsu Chemical Co., Ltd.) W-5: Surflon S-382 (Asahi Glass Co., Ltd.) Made)

[0265]

[Table 8]

[0266]

[Table 9]

[0267]

[Table 10]

[0268]

[Table 11]

[0269]

[Table 12]

[0270]

[Table 13]

[0271]

[Table 14]

From the results shown in Tables 8 to 14, it is understood that the positive resist composition of the present invention provides a rectangular pattern profile with high sensitivity and high resolution, and is extremely excellent in PCD and PED stability.

Examples 1, 4, 5, 14, 15, 20, 2
In 1, 29, 30, and 31, the organic basic compound was changed from B-1 to B-2, B-3, B-4, B-
5 and the same performance was obtained.
Examples 1, 4, 5, 14, 15, 20, 21, 2
In 9, 30, and 31, when the surfactant was changed from W-1 to W-2, W-3, W-4, and W-5, the same performance was obtained.

In Examples 1, 4, 6, 8, 13, and 14, when PHS-2 was changed to PHS-4 and the same operation was performed, equivalent performance was obtained. In Example 41, the binders were (c-21) ′ and (c-2), respectively.
2) ', (c-28)', (c-30) ', (c-33)'
The same performance was obtained by changing to. Further, in the example, when PHS-1 was changed to PHS-3 and the same operation was performed, equivalent performance was obtained.

Examples 1, 4, 5, 14, 15, 20, 3
In 9, 40, and 41, when the solvent was changed to propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20 (weight ratio), the same effect was obtained.

In Examples 1, 5, 11, and 28,
The acid generators were (I-1), (I-7), (I-
8), (I-9) and (II-3) were carried out, and the same performance was obtained.

Further, the components shown in Table 1 were dissolved in the above solvent, and the composition solutions of Examples 1 to 31 and 35 were filtered through a 0.1 μm polyethylene filter to prepare a resist solution. The in-plane uniformity of each of these resist solutions was evaluated as described below.

(In-plane uniformity) Each resist solution was 8 in.
h. A resist coating film for measuring in-plane uniformity was obtained by coating on a silicon wafer and performing the same processing as the coating of a resist layer as described above. This is a Dainippon Screen Lambd
At aA, the coating film thickness was measured at 36 points evenly so as to form a cross along the wafer diameter direction. The standard deviation of each measured value is taken.
The above was evaluated as x. As a result, those using propylene glycol monomethyl ether acetate (PGMEA) as a resist coating solvent (Examples 1 to 3)
In 1), the in-plane uniformity was ○. On the other hand, in the case of using ethyl lactate (EL) as the resist coating solvent (Example 35), the in-plane uniformity was x. Therefore, it is understood that PGMEA is preferably used as a resist coating solvent in the present invention.

(6) Patterning by 1: 1 X-ray Exposure Using each of the resist compositions of Example 42 and Comparative Examples 1 and 2, a film thickness of 0.40 μm was obtained in the same manner as the resist film B of (1). Was obtained. Next, patterning is performed in the same manner as in the above (2) except that a 1: 1 X-ray exposure apparatus (gap value: 20 nm) is used, and the resist performance (sensitivity, resolution, and pattern shape) is obtained in the same manner as in the above (3). ) Was evaluated. Table 15 shows the evaluation results.

Table 15 Resist Composition Sensitivity (mJ / cm ² ) Resolution (μm) Pattern Shape Example 42 50 0.10 Rectangular Comparative Example 1 185 0.18 Tapered Shape, Film Loss Comparative Example 2 185 0.18 Tapered Shape

As is clear from Table 15, it can be seen that the resist composition of the present invention shows extremely excellent performance even in X-ray exposure.

[0282]

Industrial Applicability The positive chemically amplified resist composition of the present invention has high sensitivity and high resolution, can provide an excellent rectangular pattern profile, and can also provide PCD and PE.
D is extremely excellent in stability and applicability.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R (72) Inventor Ichihei Nakamura 4000 Kawajiri, Yoshida-cho, Harihara-gun, Shizuoka Prefecture Fujisha Shin-Film Co., Ltd. F-term (reference) 2H025 AA01 AA02 AA03 AA11 AB16 AC05 AC06 AD03 BE00 BE10 BG00 CA00 CA14 CB41 CC20 FA12 FA17 4J002 BC111 BC121 BG031 BG071 BH011 EB026 EB106 EB117 EB0 E080 EE038 EU217 EV026 EV046 EV048 EV208 EV226 EV227 EV228 EV237 EV257 EV267 EV297 EV307 EV317 EW046 EX036 GP03

Claims (6)

[Claims] 1. A positive chemically amplified resist composition comprising (a) a compound which directly or indirectly generates a radical (A) upon irradiation with energy rays. 2. The positive chemically amplified resist composition according to claim 1, further comprising (b) a compound which generates an acid upon irradiation with energy rays. 3. A resin having a group decomposable by an acid and having increased solubility in an alkali developer due to the action of an acid, or (g) a resin insoluble in water and soluble in an alkali developer. The positive chemically amplified resist composition according to claim 1, further comprising: 4. A low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has (f) a group decomposable by an acid and whose solubility in an alkali developing solution is increased by the action of an acid. Item 4. A positive chemically amplified resist composition according to any one of Items 1 to 3. 5. The method according to claim 1, wherein the radical (A) reacts with (a) the compound (a) which generates an acid upon irradiation with energy rays to generate an acid. The positive chemically amplified resist composition as described in the above. 6. The positive chemically amplified resist composition according to claim 1, wherein the compound (a) is at least one selected from the following group. Alkyl halide other than fluorine, aryl halide other than fluorine, halogen aralkyl other than fluorine,
Allyl halides other than fluorine (however, in the above alkyl, aryl, aralkyl, and allyl groups, some or all of the hydrogens may be substituted with fluorine), thiol compounds, secondary alcohols, allyls which may have a substituent Alcohols, benzyl alcohols which may have a substituent on the aromatic ring, and their esters, ether compounds, sulfide compounds, disulfide compounds, halogenated silicon compounds, alkoxysilicon compounds, linear, branched or cyclic acetal compounds N- Hydroxyl compound