JP2002278052A - Positive type resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type electron beam or X-ray resist composition having high sensitivity and high resolving power, capable of giving a pattern profile with superior rectangularity and excellent in PBD stability. SOLUTION: The positive type electron beam or X-ray resist composition contains a compound of formula (I), (II) or (III) which generates an acid when irradiated with radiation, a cyclic ether compound and an organic basic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type electron beam or X-ray resist composition, and more particularly to a pattern profile obtained by exposure to an electron beam or X-ray, high sensitivity, excellent resolution, and PBD stability. The present invention relates to a positive electron beam or X-ray resist composition having excellent properties. Here, PBD (Post B
ake Delay) stability means heating operation after irradiation (Post Expo
It is the storage stability when left in the irradiation device or outside the device from the time of sure bake) to the time of development.

[0002]

2. Description of the Related Art Resists for electron beam lithography and resists for X-ray lithography are characterized by high resolution compared to resists for optical lithography such as i-line resist, KrF excimer laser resist and ArF excimer laser resist. However, low throughput is a problem. Therefore, the emergence of a highly sensitive resist while maintaining a high resolution is desired. Further, there has been a problem that the storage stability (PBD stability) when left untreated from the heating operation after irradiation to the development is deteriorated.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a PBD (Post Bake Delaware) having high sensitivity and high resolution.
y) It is to provide a positive electron beam or X-ray resist composition having excellent stability.

[0004]

That is, according to the present invention,
The following positive electron beam or X-ray resist composition is provided to achieve the above object of the present invention.

(1) A positive electron beam characterized by containing (a) a compound which generates an acid upon irradiation with an electron beam or X-ray, (b) a cyclic ether compound, and (f) an organic basic compound. Or an X-ray resist composition. (2) (a) the compound that generates an acid upon irradiation with an electron beam or X-ray contains at least one of the compounds represented by the following general formulas (I) to (III). The positive electron beam or X-ray resist composition according to the above (1).

[0006]

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(Wherein R _{1 to} R ₃₇ 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 an -S-R ₃₈ group .R
₃₈ represents a linear, branched or cyclic alkyl group or an aryl group. Also, R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , R ₂₈ to
Two or more of R ₃₇ may combine to form a ring containing one or more selected from a single bond, carbon, oxygen, sulfur, and nitrogen. X ⁻ represents an anion of an alkylsulfonic acid, a benzenesulfonic acid, a naphthalenesulfonic acid or an anthracenesulfonic acid, which may have a substituent. )

(3) In the general formulas (I) to (III), X
^- is at least one fluorine atom, at least one fluorine atom in the substituted straight-chain, branched or cyclic alkyl group, substituted with at least one fluorine atom, straight chain, branched and cyclic alkoxy Group, acyl group substituted with at least one fluorine atom, acyloxy group substituted with at least one fluorine atom, sulfonyl group substituted with at least one fluorine atom, substituted with at least one fluorine atom A sulfonyloxy group, a sulfonylamino group substituted with at least one fluorine atom,
An aryl group substituted with at least one fluorine atom,
Alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid or at least one group selected from an aralkyl group substituted with at least one fluorine atom and an alkoxycarbonyl group substituted with at least one fluorine atom; The positive electron beam or X-ray resist composition according to the above (2), which is an anthracene sulfonic acid anion.

(4) (c) a resin having a group decomposable by an acid, whose solubility in an alkali developing solution is increased by the action of an acid; and (d) a group decomposable by an acid,
The solubility in an alkali developing solution is increased by the action of an acid, and the composition according to any one of the above (1) to (3), which contains at least one of low-molecular-weight dissolution inhibiting compounds having a molecular weight of 3000 or less. The positive electron beam or X-ray resist composition according to the above.

(5) The above (1) to (4), further comprising a fluorine-based and / or silicon-based surfactant.
The positive electron beam or X-ray resist composition according to any one of the above. (6) The above-mentioned (1), which mainly contains propylene glycol monomethyl ether acetate as a solvent.
The positive electron beam or X-ray resist composition according to any one of (1) to (5).

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the electron beam resist. As a result, a positive resist composition containing (b) a cyclic ether compound and (f) an organic basic compound was obtained. The inventors have found that the above problems can be solved, and have achieved the present invention. Furthermore, X
It has been found that it is also useful as a resist composition for lines. The present invention is characterized in that it does not require an acidic group and contains a cyclic ether compound. The present invention focuses on electron beam or X-ray irradiation itself, and by containing a cyclic ether compound, has surprisingly been able to solve the above-mentioned various problems inherent in an electron beam resist. This is not known at all.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The positive electron beam or X-ray resist composition of the present invention will be described below. (B) Cyclic ether compound The (b) cyclic ether compound used in the present invention includes compounds such as dioxane such as 4-phenyl-1,4-dioxane and oxetane such as 3,3-bischloromethyloxetane. Can be used. Further, glycidyl ethers such as allyl glycidyl ether and phenyl glycidyl ether, glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, bisphenol A type epoxy resins and tetrabromobisphenol A type epoxy resins commercially available under the trade name of Epicoat, Compounds such as bisphenol F type epoxy resin, phenol novolak type epoxy resin, and cresol novolak type epoxy resin can be used. Further, as the cyclic ether compound (b), a compound having a partial structure represented by the following general formulas (X) and (Y) is more preferable in that the effects of the present invention are more remarkably exhibited.

[0013]

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

In the general formulas (X) and (Y), R _a ,
When R _b , R _c , R _{c ′} and R _{c ″} are an aryl group, generally 4
Having ~ 20 carbon atoms, an alkyl group, an aryl group,
It may be substituted by an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylmercapto group, an aminoacyl group, a carboalkoxy group, a nitro group, a sulfonyl group, a cyano group or a halogen atom. Here, examples of the aryl group having 4 to 20 carbon atoms 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 _a , R _b , R _c , R _{c ′} , and R _{c ″} represent an alkyl group, a saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms. Represents a halogen atom,
It may be substituted by a cyano group, an ester group, an oxy group, an alkoxy group, an aryloxy group or an aryl group. Here, as a saturated or unsaturated linear, 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, a t-butyl group , Pentyl, isopentyl, neopentyl, hexyl, isohexyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, vinyl, propenyl, butenyl, 2 -Butenyl group, 3-butenyl group, isobutenyl group, pentenyl group, 2-pentenyl group, hexenyl group, heptenyl group,
Examples thereof include an octenyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopentenyl group, and a cyclohexenyl group.

Further, a saturated or olefinically unsaturated ring formed by bonding any two of R _a , R _b , R _c , R _{c ′} , and R _{c ″} , specifically, cycloalkane or cycloalkane The alkene usually represents 3 to 8, preferably 5 or 6 ring members. As the divalent linking group for L, a single bond, an optionally substituted alkylene group, a cycloalkylene group, or an arylene group, or —O—, —O—CO—R
_a1- , -CO- _ORa2- , -CO-N ( _Ra3 ) _-Ra4
Represents-. R _a1 , R _a2 , and R _a4 may be the same or different and may have a single bond, or an ether structure, an ester structure, an amide structure, a urethane structure, or a ureide structure, and may have a substituent. Good represents an alkylene group, a cycloalkylene group, or an arylene group. R _a3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group which may have a substituent.

In the present invention, in the general formulas (X) and (Y), it is preferable that R _a , R _b , R _c , R _{c ′} , and R _{c ″} be a hydrogen atom or a _C 1 to _C 4. It is an alkyl group.

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

[0020]

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[0021]

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[0022]

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[0023]

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In the resist composition of the present invention, the cyclic ether compound (preferably the compound represented by the above general formulas (X) and (Y)) is added in an amount based on the total weight (solid content) of the composition. It is preferably 0.5 to 50% by weight, more preferably 3 to 30% by weight.

(F) Organic Basic Compound The (f) organic basic compound 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.

[0026]

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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 (f) organic basic compounds, guanidine, 1,1-dimethylguanidine,
1,3,3, -tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine,
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-imino Piperidine, 1- (2-
Aminoethyl) 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,
-Pyrazoline, 3-pyrazolin, N-aminomorpholine, N- (2-aminoethyl) morpholine, diazabicyclononene, 1,8-diazabicyclo [5.4.0]
Undec-7-ene, 1,5-diazabicyclo [4.
3.0] non-5-ene, 2,4,5-triphenylimidal, and the like. Of these, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,1
5-diazabicyclo [4.3.0] non-5-ene,
Examples thereof include 2,4,5-triphenylimidal and the like, but are not limited thereto.

These (f) organic basic compounds can be used alone or in combination of two or more.
The amount of the organic basic compound used is usually based on (a) the compound that generates an acid upon irradiation with an electron beam or X-ray of the present invention.
It is 0.01 to 10 mol%, preferably 0.1 to 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.

(A) Compound that generates an acid upon irradiation with an electron beam or X-ray (hereinafter also referred to as “component (a)”) As the component (a), a compound which generates an acid upon irradiation with an electron beam or X-ray Any of these can be used, but the compounds represented by the above general formulas (I) to (III) are preferred. Hereinafter, the compounds represented by formulas (I) to (III) will be described in detail.

In the general formulas (I) to (III), R _{1 to} R
The linear or branched alkyl group of ₃₈ may have a substituent and may have a carbon number such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. 1-4 are mentioned. 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 ₃₇ include a methoxy group, an ethoxy group,
Those having 1 to 4 carbon atoms such as a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group are exemplified. Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. R _{1 to} R ₃₇
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group for R ₃₈ include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. Preferred as these substituents are alkoxy groups having 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, iodine atom), aryl groups having 6 to 10 carbon atoms, and alkenyl groups having 2 to 6 carbon atoms. , A cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, a nitro group and the like.

Further, R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , R _{28 to} R
Of _37, two or more of formed by combining a single bond, carbon, oxygen, one selected sulfur, and nitrogen or 2
Examples of the ring containing more than one kind include a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, a pyrrole ring, and the like.

In the general formulas (I) to (III), X ^- is
An anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid, which may have a substituent. The substituent is preferably at least one selected from the following. 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, An acyl group substituted with one fluorine atom, an acyloxy group substituted with at least one fluorine atom, a sulfonyl group substituted with at least one fluorine atom,
A sulfonyloxy group substituted with at least one fluorine atom, a sulfonylamino group substituted with at least one fluorine atom, an aryl group substituted with at least one fluorine atom, and an aralkyl substituted with at least one fluorine atom Group and an alkoxycarbonyl group substituted by 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, 2,2,2
Examples thereof include a 2-trifluoroethyl group, a heptafluoropropyl group, a heptafluoroisopropyl group, a perfluorobutyl group, a perfluorooctyl group, a perfluorododecyl group, and a perfluorocyclohexyl group. Above all,
A perfluoroalkyl group having 1 to 4 carbon atoms, all substituted with fluorine, is preferred.

The linear, branched or cyclic alkoxy group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specific examples include a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoroisopropyloxy group, a perfluorobutoxy group, a perfluorooctyloxy group, a perfluorododecyloxy group, and a perfluorocyclohexyloxy group. 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 1 to 1 carbon atoms.
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 with 1 to 25 fluorine atoms. Specific examples include a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a pentafluorophenoxycarbonyl group, a perfluorobutoxycarbonyl group, and a perfluorooctyloxycarbonyl group.

[0044] The most preferred X ^- is a fluorine-substituted benzenesulfonic acid anion, among others pentafluorobenzenesulfonic acid anion is particularly preferred.

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

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

[0047]

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[0048]

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

[0050]

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

[0052]

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

The compounds of the general formulas (I) and (II) can be obtained by reacting an aryl Grignard reagent such as aryl magnesium bromide with a substituted or unsubstituted phenylsulfoxide to give the resulting triarylsulfonium halide with the corresponding sulfone. A method of performing salt exchange with an acid, a method of subjecting a substituted or unsubstituted phenyl sulfoxide and a corresponding aromatic compound to condensation and salt exchange using an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride,
Alternatively, it can be synthesized by a method of condensation and salt exchange between a diaryliodonium salt and a diaryl sulfide using a catalyst such as copper acetate. The compound of the formula (III) 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, specific methods for synthesizing specific compounds of the general formulas (I) to (III) 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 Triphenylsulfonium pentafluorobenzenesulfonate: Synthesis of Specific Example (I-1)) Diphenylsulfoxide 509 was converted to benzene 800 m
1 and 200 g of aluminum chloride was added thereto and refluxed for 24 hours. The reaction solution was slowly poured into 2 L of water, and 400 ml of concentrated hydrochloric acid was added thereto, followed by heating at 70 ° C. for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate,
After filtration, 200 g of ammonium iodide was added to 400 m of water.
The solution dissolved in 1 was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodide. 30.5 g of triphenylsulfonium iodide was added to 1000 ml of methanol.
And 19.1 g of silver oxide was added to the solution, followed by stirring at room temperature for 4 hours. The solution was filtered, and an excess amount of the solution of tetramethylammonium pentafluorobenzenesulfonate synthesized above was added thereto. The reaction solution was concentrated, and this was dissolved in 500 ml of dichloromethane.
% Tetramethylammonium hydroxide aqueous solution and water. After drying the organic phase over anhydrous sodium sulfate,
Concentration provided triphenylsulfonium pentafluorobenzenesulfonate.

(Synthesis of Triarylsulfonium Pentafluorobensene Sulfonate: Specific Examples (I-9) and (II)
Synthesis of mixture with -1)) 50 g of triarylsulfonium chloride (50% aqueous solution of triphenylsulfonium chloride, manufactured by Fluka) is dissolved in 500 ml of water, and an excess amount of a solution of pentafluorobenzenesulfonic acid tetramethylammonium salt is added thereto. And an oily substance precipitated. The supernatant was removed by decantation, and the obtained oily substance was washed with water and dried to obtain triarylsulfonium pentafluorobenzensulfonate (specific examples (I-9) and (II-1)).
) As a main component.

(Synthesis of di (4-t-amylphenyl) iodonium pentafluorobensensulfonate: Synthesis of Specific Example (III-1)) 60 g of t-amylbenzene, 39.5 g of potassium iodate, 81 g of acetic anhydride, 170 ml of dichloromethane And 66.8 concentrated sulfuric acid under ice-cooling.
g was slowly added dropwise. 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.

In the present invention, as the component (a), a compound which decomposes upon irradiation with an electron beam or X-ray to generate an acid other than the compounds represented by the above general formulas (I) to (III) is used. You can also. In the present invention, as the component (a), together with the compounds represented by the above general formulas (I) to (III), a compound which is decomposed by irradiation with another electron beam or X-ray to generate an acid May be used in combination. The amount of the acid generator which can be used in combination with the compounds represented by the above general formulas (I) to (III) when used in combination is usually in a molar ratio (component (a) / other acid generator). 100/0
20/80, preferably 100/0 to 40/60, and more preferably 100/0 to 50/50. The total content of the component (a) is usually 0.1 to 20 with respect to the solid content of the whole positive electron beam or X-ray resist composition of the present invention.
%, Preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight.

Other acid generators that can be used as component (a) in the present invention include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, or Known compounds capable of generating an acid upon irradiation with an electron beam or X-ray used for a micro resist or the like and a mixture thereof can be appropriately selected and used.

For example, SISchlesinger, Photogr.Sci.E
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No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
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Nos. 4,069,055 and 4,069,056, and phosphonium salts described in JVCrivello et al., Macromorecules, 10 (6), 1307 (19
77), 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),
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No. 7, Dokoku Patent Nos. 2,904,626, 3,604,580, 3,60
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Selenonium salts, CSwen et al, Teh, Proc.Co
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lins et al., J. Chem.SoC., Perkin I, 1695 (1975), M. Rudins
tein etal, Tetrahedron 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
ihan etal, Macormolecules, 21, 2001 (1988), PMCollins
etal, J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase
etal, Macromolecules, 18, 1799 (1985), E. Reichmanis eta
l, J.Electrochem.Soc., Solid State Sci.Technol., 130
(6), FM Houlihan et al, 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
Acid generator having an o-nitrobenzyl-type protecting group described in No. 33022, etc., M. TUNOOKA et al., Polymer Preprints Japa
n, 35 (8), G.Berner et al., J.Rad.Curing, 13 (4), WJMijs
etal, Coating Technol., 55 (697), 45 (1983), Akzo, H.Adac
hi etal, Polymer Preprints, Japan, 37 (3), European Patent No.
0199,672, 84515, 199,672, 044,115,
No. 0101,122, U.S. Pat.Nos. 618,564, 4,371,605,
No. 4,431,774, JP-A-64-18143, JP-A-2-245756
And compounds that generate sulfonic acid upon photolysis, such as iminosulfonate described in Japanese Patent Application No. 3-140109, and disulfone compounds described in JP-A-61-166544. .

Further, a compound in which a group or a compound which generates an acid upon irradiation with these electron beams or X-rays is introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse e.
tal, J. Am. Chem. Soc., 104, 5586 (1982), SPPappas eta
l, J.Imaging Sci., 30 (5), 218 (1986), S.Kondo et al., Mak
romol.Chem., Rapid Commun., 9,625 (1988), Y.Yamadaeta
l, Makromol. Chem., 152, 153, 163 (1972), JVCrivello
etal, J. Polymer Sci., Polymer Chem. Ed., 17, 3845 (197
9), U.S. Patent No. 3,849,137, Dokoku Patent No. 3,914,407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263
No., JP-A-63-146038, JP-A-63-163452, JP-A-63-163452
Compounds described in JP-A-62-153853 and JP-A-63-146029 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 compounds capable of decomposing upon irradiation with an electron beam or X-ray to generate an acid, 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).

[0065]

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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.

[0067]

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[0068]

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[0069]

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(2) An iodonium salt represented by the following formula (PAG3) or a sulfonium salt represented by the following formula (PAG4).

[0071]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

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.

[0074] Z ^- represents a counter anion, for example BF ₄ ^-,
Condensed polynuclear aromatic sulfonic acid anions such as alkane sulfonic acid anion, benzene sulfonic acid anion, naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, sulfonic acid group-containing dye, and the like, but are not limited thereto. is not.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent. Specific examples include the following compounds, but are not limited thereto.

[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok eta
l, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Po
Chem. Ed., 18,2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

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

[0089]

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Where 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.

[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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

(C) having an acid-decomposable group,
Trees whose solubility in potash developer is increased by the action of acids
Fat In the positive electron beam or X-ray resist composition of the present invention
As the component (c) used, the main chain or side chain of the resin,
Alternatively, an acid-decomposable group is provided on both the main chain and the side chain.
Resin. Of these, the groups decomposable by acid are added to the side chain.
Is more preferable. Good as an acid-decomposable group
A preferred group is -COOA⁰, -OB⁰Group
As a group containing these, -R⁰-COOA⁰Or -A_r
-OB⁰The group shown by these is mentioned. Where A⁰Is-
C (R⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹) (R⁰²)
(R^{0 Three}) Or -C (R⁰⁴) (R⁰⁵) -OR⁰⁶Base
Show. B⁰ Is A⁰ Or -CO-OA⁰Indicates a group
(R⁰, R⁰¹~ R⁰⁶, And Ar are as defined 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.

Next, as the base resin when the groups decomposable by these acids are bonded as side chains, -OH or -COOH, preferably -R ⁰ -COOH or -A _r -OH groups are added to the side chains. 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 with a 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.) and measured at 170 ° C.
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 (c) 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.

Hereinafter, specific examples of the component (c) used in the present invention will be shown, but the present invention is not limited thereto.

[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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The content of acid-decomposable groups is determined by the number of acid-decomposable groups (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S) in the resin. 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 (c) 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. 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, defocus latitude, etc.).
Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography. Further, the component (c) may be used in combination of two or more kinds.

(D) Low-molecular acid-decomposable dissolution inhibiting compound (“(d) component”) In the present invention, the (d) component may be used. The component (d) has a group that can be decomposed by an acid, and has a molecular weight of 300, in which the solubility in an alkali developer is increased by the action of an acid.
It is a low molecular weight dissolution inhibiting compound of 0 or less. The preferred component (d) 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 (d) has at least two groups capable of being decomposed by an acid in its structure, and at a 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 (d) 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.

[0113]

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The acid-decomposable dissolution-inhibiting compound as the component (d) may have a plurality of acid-decomposable groups on one benzene ring, but preferably has one acid-decomposable group 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,
A group which can be decomposed by, ie, -COO-A⁰ , -OB⁰
As a group containing a group, -R⁰-COO-A⁰Or -Ar
-OB⁰The group shown by these is mentioned. Where A⁰Is-
C (R⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹) (R⁰²)
(R^{0 Three}) Or -C (R⁰⁴) (R⁰⁵) -OR⁰⁶Base
Show. B⁰Is A⁰Or -CO-OA⁰Represents a group.
R⁰¹, R⁰², R⁰³, R⁰⁴And R⁰⁵Are the same
They may be different and include a hydrogen atom, an alkyl group,
A alkyl group, an alkenyl group or an aryl group;
⁰⁶Represents an alkyl group or an aryl group. Where R⁰¹
~ R⁰³At least two are groups other than a hydrogen atom,
Also, R⁰¹~ R⁰³, And R⁰⁴~ R⁰⁶Two of the groups are bonded
To form a ring. R⁰May have a substituent
Shows a good divalent or higher valent aliphatic or aromatic hydrocarbon group
And -Ar- has a monocyclic or polycyclic substituent,
Represents a divalent or higher valent aromatic group.

The alkyl group preferably has 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. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, aralkyloxy groups, acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, and valeryl group. Group, an acyloxy group such as a butyryloxy group, the above alkenyl group, a vinyloxy group.
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group, and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a 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 (d), 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,
Japanese Patent Application No. 4-107889, groups shown above some or all of the phenolic OH groups of the polyhydroxy compounds described herein, such as Nos. 4-152195, -R ⁰ -
COO-A ⁰ or B ⁰ groups and protected compounds are included.

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.

[0121]

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[0122]

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[0123]

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[0124]

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Here, R¹⁰¹ , R¹⁰² , R¹⁰⁸ , R¹³⁰ : Same but different
May be a hydrogen atom, -R⁰-COO-C (R⁰¹) (R
⁰²) (R⁰³) Or -CO-OC (R⁰¹) (R^{0 Two}) (R
⁰³) Where R⁰, R⁰¹, R⁰²And R⁰³Is defined as above
Is the same.

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

[0127]

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Here, G = 2 to 6 where G = 2
R¹⁵⁰ , R¹⁵¹ At least one of which is an alkyl group;¹⁵⁰ , R¹⁵¹ : Hydrogen source, which may be the same or different
, An alkyl group, an alkoxy group, -OH, -COOH,
-CN, halogen atom, -R¹⁵² -COOR^{15 Three} If
Is -R¹⁵⁴ -OH, R¹⁵² , R¹⁵⁴ : Alkylene group, R¹⁵³ : Hydrogen atom, alkyl group, aryl group, or
Aralkyl group, R⁹⁹, R¹⁰³ ~ R¹⁰⁷ , R¹⁰⁹ , R¹¹¹ ~ R¹¹⁸ , R
¹²¹ ~ R^{one two Three} , R¹²⁸ ~ R¹²⁹ , R¹³¹ ~ R¹³⁴ , R
¹³⁸ ~ R¹⁴¹ And R¹⁴³ : Water may be the same or different
Element atom, hydroxyl group, alkyl group, alkoxy group, acyl
Group, acyloxy group, aryl group, aryloxy group,
Aralkyl group, aralkyloxy group, halogen atom, nitro
B, carboxyl group, cyano group, or -N (R
¹⁵⁵) (R¹⁵⁶) (Where R¹⁵⁵ , R¹⁵⁶ : H, alkyl
Group or aryl group) R¹¹⁰ : Single bond, alkylene group, or

[0129]

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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

[0132]

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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, z1, a
2, at least one of 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 the general formula [V]
In the case of (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 + l
1), (i1 + m1), (o1 + q1), (s1 + u1) ≦ 5.

[0134]

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[0135]

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[0136]

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[0137]

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Specific examples of preferred compound skeletons are shown below.

[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

[Of 60]

[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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

[0153]

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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.

In the present invention, (e)
Resins that are insoluble in water and soluble in alkaline developer
"(E) component" or "(e) alkali-soluble resin"
) Can be used. In the positive electron beam or X-ray resist composition of the present invention, as the component (e), a resin that is insoluble in water and soluble in an aqueous alkaline solution can be used. When the component (e) is used, it is not always necessary to incorporate a resin having a group that is decomposed by the action of the acid (c) and increases the solubility in an alkali developer. Of course, it does not exclude the combination with the component (c). Examples of the (e) alkali-soluble resin used in the present invention include novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, and hydrogenated polyhydroxy resin. Styrene, halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o /
p- and m / p-hydroxystyrene copolymers, partially O-alkylated compounds based on hydroxyl groups of polyhydroxystyrene (for example, 5 to 30 mol% of O-methylated products, O-
(1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O-
(T-butoxycarbonyl) methylated compound) or O
-Acylated products (e.g., 5 to 30 mol% o-acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene -Hydroxystyrene copolymers, carboxyl group-containing methacrylic resins and derivatives thereof, and polyvinyl alcohol derivatives, but are not limited thereto. Particularly preferred (e) alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, and a part of O-polystyrene. Alkylation or O-
Acylated product, styrene-hydroxystyrene copolymer,
α-methylstyrene-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 as a mixture 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 forms, for example, 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 weight average molecular weight of the novolak resin thus obtained is preferably 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 (e) 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 shown below. However, the content of the present invention is not limited to these. 1) A positive electron beam or X-ray resist composition containing the above component (a), the above component (b) and the above component (c). 2) The component (a), the component (b), and the component (d)
And a resist composition for a positive electron beam or X-ray, comprising the component (e). 3) Component (a), Component (b), Component (c)
And a resist composition for a positive electron beam or X-ray, comprising the above component (d).

In each of the above constitutional examples, the amount of the component (c) of 1), the component (e) of 2) and the component (c) 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 90% by weight. The amount of the component (d) used in the composition is 3 to 45 parts with respect to the solid content of the whole composition in each of the above constitution examples.
%, More preferably 5 to 30% by weight, even more preferably 10 to 20% by weight.

The positive electron beam or X-ray resist composition of the present invention may further contain, if necessary, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, and a phenol for accelerating the solubility in a developing solution. A compound having two or more acidic OH groups 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 (e) the alkali-soluble resin. 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 a phenol compound having a molecular weight of 1,000 or less can be prepared by, for example, referring to the methods described in JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. ,
It can be easily synthesized by those skilled in the art. 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, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethyl Formamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable. Or in combination can be used. 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 essential performance such as high resolution, sensitivity, applicability, minimum application amount, adhesion to substrates, heat resistance, and storage stability of the composition Therefore, high performance compositions are required from various viewpoints.
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. In particular, in the case of an electron beam or X-ray resist, since exposure is performed under a high vacuum in an electron beam irradiation apparatus, there is a concern that throughput may be reduced in consideration of evacuation time and the like, and a situation in which coating is performed on a wafer having a larger diameter may occur. Will increase. 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.
The following is more preferred.

In the invention, a fluorine-based and / or silicon-based surfactant can be used. For example,
F-top EF301, EF303 (Shin-Akita Chemical Co., Ltd.)
Co., Ltd.), Florado FC430, 431 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, F17
6, F189, F08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC-101, 102, 103, 1
Fluorinated surfactants such as 04, 105, and 106 (manufactured by Asahi Glass Co., Ltd.) and silicon-based surfactants. Further, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the silicon-based surfactant. Surfactants other than fluorine-based and / or silicon-based surfactants can also 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 or methacrylic acid (Co) polymerized polyflow no. 75, N
o. 95 (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 entire composition in the composition of the present invention. These surfactants may be added alone or in combination of two or more.

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 Corporation, Posidyne, Nylon Falcon, and the like. Also,
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 0.100μ
m) 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 filter having a pore diameter of 0.1 μm.

A positive electron beam or X-ray resist composition of the present invention is spinner-coated on a substrate (eg, silicon / silicon dioxide coating) such as used in the manufacture of precision integrated circuit devices.
After coating by an appropriate coating method such as a coater or the like, exposure is performed through a predetermined mask, baking and development are performed, whereby 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, aqueous ammonia and the like, and ethylamine, n-propylamine and the like. 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.

[0172]

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-800 manufactured by Nippon Soda Co., Ltd.)
0) 10 g was dissolved in 50 ml of pyridine, and 3.63 g of di-t-butyl dicarbonate was added dropwise thereto with stirring at room temperature. After stirring at room temperature for 3 hours, the mixture was added dropwise to a solution of 1 L of ion-exchanged water / 20 g of concentrated hydrochloric acid. The precipitated powder was filtered, washed with water, and dried to obtain Resin Example (c-3).

[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 in 80 ml of THF.
, And 0.01 g of p-toluenesulfonic acid was added thereto and reacted at room temperature for 18 hours. The reaction solution was distilled water 5
L was dripped with vigorous stirring, and the precipitated powder was filtered,
After drying, a resin example (c-33) was obtained.

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

(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: Compound)
Synthesis of 41) 1,3,3,5-tetrakis- (4-hydrido)
Roxyphenyl) pentane in 44 g of N, N-dimethyla
Dissolve in 250 ml of Cetamide and add potassium carbonate
70.7 g and then 90.3 g of t-butyl bromoacetate
The mixture was stirred at 120 ° C. for 7 hours. Ionize the reaction mixture
The mixture was poured into 2 liters of exchanged water, and the obtained viscous material was washed with water. this
Was purified by column chromatography to give Compound Example 4.
1 (R is all -CH _Two COOC_Four H₉ (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.

(Synthesis Example of Cyclic Ether Compound) (Synthesis Example 1) Synthesis of Compound A-3 13.25 g (0.05 mol) of trimesic acid chloride and 18.35 g (0.1 mol) of tetrahydrofurfuryl alcohol
8 mol) was dissolved in 150 ml of tetrahydrofuran. 20.23 g (0.20 mol) of triethylamine was slowly dropped, and the mixture was stirred at room temperature for 2 hours. Ethyl acetate /
Extraction with water, washing with water and drying under reduced pressure gave 20.23 g of compound A-3 as a white solid. Similarly, compounds A-1, A-2 and A-4 to A-6 were synthesized.

[0182]

Embedded image

Examples [Examples and Comparative Examples] (1) Coating of resist The components shown in Table 1 below were dissolved in 8.2 g of propylene glycol monomethyl ether acetate, and this was dissolved in 0.1 g of propylene glycol monomethyl ether acetate.
The solution was filtered through a 1 μm Teflon (registered trademark) filter to prepare a resist solution. The composition of Example 21 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 suction type hot plate at 120 ° C. for 90 seconds to obtain a 0.5 μm-thick resist film. (2) Preparation of resist pattern An electron beam lithography system (pressing voltage 50 Ke
Irradiation was performed using V). 110 ° C each after irradiation
Heating for 60 seconds with a vacuum adsorption type hot plate,
It was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The cross-sectional shape of the obtained contact hole pattern was 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.

(4) Evaluation of PBD The resist film obtained by the method (1) was irradiated with an electron beam lithography apparatus (acceleration voltage: 50 keV). After the irradiation, heating was performed for 60 seconds on a vacuum suction type hot plate at 110 ° C., and after leaving for 120 minutes, 2.38%
It was immersed in a TMAH aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried. The cross-sectional shape of the obtained contact hole pattern was observed with a scanning electron microscope. The minimum pattern size that can be resolved with the same irradiation dose as the minimum irradiation dose obtained by the method (3) is obtained. If the size and the limit resolution obtained in (3) are within 3%, the PBD stability is passed (o). Those exceeding 3% and within 5% are regarded as PBD stability tolerance (△). If it exceeds 5%, PBD stability is not possible (x).

[0186]

[Table 1]

The acid generator PAG-1 is as follows.

[0188]

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 13000, molecular weight distribution (Mw /
Mn) 1.4 (c-4): p-hydroxystyrene / p- (1-ethoxyethoxy) styrene copolymer (molar ratio: 70/3)
0), weight average molecular weight 12000, molecular weight distribution (Mw /
Mn) 1.3 (c-21): p-hydroxystyrene / t-butyl methacrylate copolymer (molar ratio: 70/30), weight average molecular weight 16,000, molecular weight distribution (Mw / Mn) 2.0 (c- 22): p-hydroxystyrene / p- (1-t
-Butoxyethoxy) styrene copolymer (molar ratio: 85)
/ 15), weight average molecular weight 12000, molecular weight distribution (M
w / Mn) 1.1 (c-28): p-hydroxystyrene / p- (1-phenethyloxyethoxy) styrene copolymer (molar ratio:
85/15), weight average molecular weight 12,000, molecular weight distribution (Mw / Mn) 1.2 (c-30): p-hydroxystyrene / p- (1-phenoxyethoxyethoxy) styrene copolymer (molar ratio: 85/15) 15), weight average molecular weight 13000, molecular weight distribution (Mw / Mn) 1.2 (PHS): poly-p-hydroxystyrene (manufactured by Nippon Soda Co., Ltd., trade name VP-5000) (PHS / St: Synthesis Example 1) P-hydroxystyrene / styrene (molar ratio: 80/20), weight average molecular weight 26000, molecular weight distribution (Mw / Mn)
1.9

The organic basic compounds and surfactants used are as follows. (Organic basic compound) 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 (interfacial activity Agent) W-1: Megafac R08 (manufactured by Dainippon Ink) W-2: Megafac F-176 (manufactured by Dainippon Ink) W-3: Troysol S-366 (manufactured by Troy Chemical) W-4: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W-5: Surflon S-382 (manufactured by Asahi Glass Co., Ltd.)

[0191]

[Table 2]

From the results shown in Table 2, it is understood that the positive type electron beam resist composition of the present invention has high sensitivity, high resolution, and extremely excellent PED stability. The pattern profile was rectangular.

Further, the components shown in Table 1 were dissolved in the above solvent, and the composition liquids of Examples 1 to 30 were dissolved in 0.1 μm.
Then, the solution was filtered through a 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 applied on an 8-inch silicon wafer, and the same processing as described above for applying a resist layer was performed to obtain a resist coating film for measuring in-plane uniformity. This is a Dainippon Screen LambdaA,
The coating film thickness was uniformly measured at 36 places so as to form a cross along the wafer diameter direction. The standard deviation of each measured value was taken, and three times less than 50 were evaluated as ○, and those with 50 times or more were evaluated as x. As a result, those using propylene glycol monomethyl ether acetate (PGMEA) as a resist coating solvent (Examples 1 to 30) had in-plane uniformity of ○.

(6) Patterning by X-ray Exposure at 1: 1 Using each of the resist compositions of Example 20 and Comparative Examples 1 and 2, a resist film having a thickness of 0.40 μm was formed in the same manner as in (1). Obtained. Next, patterning is performed in the same manner as in the above (2) except that an equal-size X-ray exposure apparatus (gap value: 20 nm) is used, and the resist performance (sensitivity, resolution) and PBD stability are obtained in the same manner as in the above (3). The sex was evaluated. Table 3 shows the evaluation results. The pattern shape of Example 20 was rectangular.

Table 3 Resist Composition Sensitivity (mJ / cm ² ) Resolution (μm) PBD Stability Example 20 80 0.10 Comparative Example 1 190 0.18 × Comparative Example 2 250 0.17 ×

As is evident from Table 3, the resist composition of the present invention shows extremely excellent performance even in X-ray exposure.

[0197]

The positive electron beam or X-ray resist composition of the present invention has high sensitivity and high resolution, can provide an excellent rectangular pattern profile, and has a PBD.
Is extremely excellent in stability.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AA02 AA03 AA11 AB16 AC05 AC06 AD03 BE07 BE10 BG00 CB17 CB30 CB41 CC03 CC04 CC20 FA12

Claims (6)

[Claims] 1. A positive electron beam or X comprising (a) a compound which generates an acid upon irradiation with an electron beam or X-ray, (b) a cyclic ether compound and (f) an organic basic compound. Radiation resist composition. 2. Compounds (a) which generate an acid upon irradiation with an electron beam or X-ray are represented by the following general formulas (I) to (III):
The positive electron beam or X-ray resist composition according to claim 1, comprising at least one compound represented by the formula: Embedded image (Wherein, R _{1 to} R ₃₇ are the same or different and each represents a hydrogen atom,
Linear, it represents branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or an -S-R ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. Further, two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , and R _{28 to} R ₃₇ are combined to form one or two kinds selected from a single bond, carbon, oxygen, sulfur, and nitrogen. A ring including the above may be formed. X ⁻ represents an anion of an alkylsulfonic acid, a benzenesulfonic acid, a naphthalenesulfonic acid or an anthracenesulfonic acid, which may have a substituent. ) 3. In the general formulas (I) to (III), X
^- is at least one fluorine atom, at least one fluorine atom in the substituted straight-chain, branched or cyclic alkyl group, substituted with at least one fluorine atom, straight chain, branched and cyclic alkoxy Group, acyl group substituted with at least one fluorine atom, acyloxy group substituted with at least one fluorine atom, sulfonyl group substituted with at least one fluorine atom, substituted with at least one fluorine atom A sulfonyloxy group, a sulfonylamino group substituted with at least one fluorine atom,
An aryl group substituted with at least one fluorine atom,
Alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid or at least one group selected from an aralkyl group substituted with at least one fluorine atom and an alkoxycarbonyl group substituted with at least one fluorine atom; The positive electron beam or X-ray resist composition according to claim 2, which is an anthracene sulfonic acid anion. 4. An alkali developing solution comprising: (c) a resin having a group decomposable by an acid, whose solubility in an alkali developing solution is increased by the action of an acid; and (d) a resin having a group decomposable by an acid, 2. The composition according to claim 1, which comprises at least one of low-molecular-weight dissolution inhibiting compounds having a molecular weight of 3000 or less, the solubility of which is increased by the action of an acid.
4. The positive electron beam or X-ray resist composition according to any one of items 1 to 3. 5. The positive electron beam or X-ray resist composition according to claim 1, further comprising a fluorine-based and / or silicon-based surfactant. 6. The positive electron beam or X-ray resist composition according to claim 1, wherein the solvent mainly comprises propylene glycol monomethyl ether acetate.