JP2002229209A - Negative type resist composition for electron beam or x-ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative type chemical amplification type resist composition for electron beams or X-rays satisfying such characteristics as sensitivity, resolution and resist shape when electron beams or X-rays are used. SOLUTION: The negative type resist composition contains a compound having a disulfone group and generating an acid when irradiated with electron beams or X-rays, a resin insoluble in water and soluble in an aqueous alkali solution and a crosslinker causing crosslinking with the resin under the action of the acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative resist composition suitable for use in ultra microlithography processes such as the production of ultra LSIs and high capacity microchips, and other photofabrication processes. More specifically, the present invention relates to a negative type photoresist composition capable of forming a pattern with high definition using X-rays, electron beams and the like, and is particularly suitable for fine processing of a semiconductor device using high energy rays such as electron beams. The present invention relates to a negative resist composition which can be used for a negative resist composition.

[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 VLSI, processing of ultrafine patterns having a line width of less than half a micron is required. Have been. In order to meet the need, the wavelength of an exposure apparatus used for photolithography is becoming shorter and shorter, and now far ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been studied. . Further, formation of finer patterns by electron beams or X-rays has been studied.

In particular, electron beams or X-rays are positioned as a next-generation or next-next-generation pattern forming technology, and development of a negative resist capable of achieving a high sensitivity, a high resolution and a rectangular profile is desired. In electron beam lithography, energy is supplied to a compound in a process where an accelerated electron beam causes collision and scattering with atoms constituting a resist material to cause a reaction of the resist material to form an image. The use of a highly accelerated electron beam increases the straightness, reduces the effects of electron scattering, and makes it possible to form a high-resolution rectangular pattern.On the other hand, the electron beam permeability increases, The sensitivity decreases. As described above, in electron beam lithography, there is a trade-off between sensitivity, resolution, and resist shape, and it has been a problem how to achieve both. As a resist material for these, for the purpose of improving sensitivity, a chemically amplified resist mainly using an acid catalyzed reaction is used, and as a main component for a negative resist, an alkali-soluble resin, an acid generator, and A chemically amplified composition comprising an acid crosslinking agent has been effectively used.

Conventionally, for a negative chemically amplified resist,
Various alkali-soluble resins have been proposed. For example, Japanese Patent No. 2505053, JP-A-3-170554 and JP-A-6-118646 disclose novolak-type phenol resins, JP-A-7-31463, and JP-A-8-29255.
No. 9 discloses a polyvinyl phenol resin having a narrowed molecular weight distribution, JP-A-3-87746, JP-A-8-44061 discloses a phenol resin partially converted to a cyclic alcohol structure by hydrogenation, JP-A-7-295200, Kaihei 8
JP-A-152717 discloses a resin in which a part of OH groups of polyvinyl phenol is protected by an alkyl group.
No. 86 discloses a polyvinyl phenol resin having a protecting group inactive to an acid such as an acyl group. JP-A-6-67431, JP-A-10-10733 discloses a polyvinylphenol resin copolymerized with styrene, and JP-A-9-166870. Discloses a polyvinylphenol resin copolymerized with (meth) acrylate monomers, and JP-A-8-240911 discloses a resin having a carboxy group.

The acid generator is disclosed in Japanese Patent Publication No. 8-36.
No. 35 discloses an organic halogen compound, JP-A-2-52348.
Nos. 4 and 5 include aromatic compounds substituted with Br and Cl.
No. 368864 and JP-A-4-366865 describe Br,
Cl-substituted aromatic compounds having alkyl or alkoxy groups, JP-A-2-150848, JP-A-6-19
No. 9770, iodonium and sulfonium compounds, JP-A-3-87746, haloalkanesulfonate compounds, JP-A-4-210960, JP-A-4-2172
No. 49, a diazodisulfone compound or a diazosulfone compound; JP-A-4-336454, Br and I-substituted alkyltriazine compounds; JP-A-4-291258, a sulfonamide, sulfonimide compound;
JP-A-291259 discloses a sulfonic acid compound of a polyhydric phenol, JP-A-4-291260 and JP-A-4-29126.
No. 1 and JP-A-6-202320 disclose a naphthoquinonediazide-4-sulfonate compound.
No. 9 discloses a disulfone compound, JP-A-6-236024 discloses an N-oxyimidosulfonate compound, and U.S. Pat. No. 5,344,742 discloses a benzylsulfonate compound.

Further, with respect to acid crosslinking agents, see JP-A-3-75.
652, JP-A-5-181277, JP-A-7-14
No. 6556, a methoxymethyl melamine compound, JP-A-4-281455, JP-A-5-232702, JP-A-6-83055, a compound having an alkoxymethyl ether group, JP-A-5-281715, an oxazine compound, JP-A-5-134412, JP-A-6-38
No. 25 discloses an aromatic compound having an alkoxyalkyl group, and JP-A-6-194838 discloses, in addition to a trioxane compound, an alkoxymethyluryl compound described in JP-A-1-293339. However, in any combination of these compounds, it is difficult to obtain a sufficiently high sensitivity under electron beam irradiation or X-ray irradiation under high accelerating voltage conditions, and the sensitivity, resolution and resist shape are satisfied. It has been a challenge to achieve both at the level they need.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problem of a technique for improving the performance in microfabrication of a semiconductor device using an electron beam or an X-ray. An object of the present invention is to provide a negative chemically amplified resist composition for electron beams or X-rays, which satisfies the characteristics of sensitivity, resolution and resist shape. Highly sensitive electron beam or X-ray that can be used in next-generation EB irradiators (EB block irradiators or EB steppers (sequential reduction projection irradiators) aimed at improving throughput) that are suitable for mass production of semiconductor devices To provide a negative type chemically amplified resist composition.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies while paying attention to the above-mentioned characteristics, and as a result, have found that the object of the present invention is excellently achieved by using the following specific compositions. Reached the present invention. That is, the present invention has the following configuration. (1) (A) a compound having a disulfone group and generating an acid upon irradiation with an electron beam or X-ray, (B) a resin insoluble in water and soluble in an aqueous alkaline solution, and (C) a compound (B) formed by the action of an acid. A negative resist composition for electron beams or X-rays, comprising: (2) The negative resist composition for electron beam or X-ray as described in (1) above, wherein (A) the compound having a disulfone group is a compound represented by the following general formula (PAG). Ra-SO ₂ -SO ₂ -Rb formula (PAG) wherein, Ra, Rb substituted or unsubstituted are each independently
Represents an aryl group, an alkyl group, a cycloalkyl group or an aralkyl group. (3) The electron beam or X according to (1) or (2), further comprising (D) an organic basic compound.
Negative resist composition for lines.

Further, the following embodiments are preferable. (4) The electron beam or the electron beam according to any one of (1) to (3), wherein the crosslinking agent of the component (C) is a hydroxymethylated, alkoxymethylated, or acyloxymethylated phenol compound. X-ray negative resist composition. (5) The crosslinking agent of the component (C) is an alkoxymethylated or acyloxymethylated melamine compound or resin, or an alkoxymethylated or acyloxymethylated urea compound or resin.
The negative resist composition for an electron beam or X-ray according to any one of (1) to (4). (6) The negative resist composition for electron beam or X-ray according to any one of (1) to (5), wherein the electron beam is irradiated under an acceleration voltage condition of 75 keV or more.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The alkali-soluble resin (B) used in the present invention includes, for example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene,
p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, polyhydroxystyrene Partial O for hydroxyl group
-Alkylated product (for example, 5 to 30 mol% of O-methylated product, O- (1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O- (t -Butoxycarbonyl) methylated product) or O-acylated product (for example, 5 to 30 mol% of 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.

The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst. As the predetermined monomer,
Cresols such as phenol, m-cresol, p-cresol, o-cresol, 2,5-xylenol,
3,5-xylenol, 3,4-xylenol, 2,3
-Xylenols such as xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenol,
pt-butylphenol, p-octylphenol,
Alkylphenols such as 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-
4-methylphenol, m-ethoxyphenol, p-
Ethoxyphenol, m-propoxyphenol, p-
Propoxyphenol, m-butoxyphenol, p-
Alkoxyphenols such as butoxyphenol, 2-
Bisalkylphenols such as methyl-4-isopropylphenol, hydroxyaromatic compounds such as m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol alone or in combination of two or more They can be used in combination, but are not limited thereto.

Examples of 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 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. (B) The alkali-soluble resin is a resin that is insoluble in water and soluble in an aqueous alkali solution (also referred to as an alkali-soluble resin). (B) The alkali dissolution rate of the alkali-soluble resin was measured with 0.261N tetramethylammonium hydroxide (TMAH) (23
° C) is preferably 20 ° / sec or more. It is particularly preferably at least 200 ° / sec (Å is Angstroms). In the present invention, these alkali-soluble resins (B) may be used in combination of two or more kinds.

The alkali-soluble resin (B) in the present invention is preferably the following alkali-soluble resin (B)
-1), an alkali-soluble resin (B-2) and an alkali-soluble resin (B-3).

Alkali-soluble resin (B-1) (B-1) contains a repeating unit containing a phenol structure having at least one OH group at the meta position, and has a molecular weight distribution in the range of 1.0 to 1.5. , Water-insoluble and soluble in alkaline aqueous solution.

Alkali-soluble resin (B-2) (B-2) The weight average molecular weight exceeds 3,000,
An alkali-soluble resin having a molecular weight of not more than 000 and satisfying the following conditions (1) and (2): (1) an aromatic ring having 6 to 20 carbon atoms and ethylene bonded directly or via a linking group to the aromatic ring; (2) The following relationship is established between the number of electrons of the π electron of the aromatic ring and the number of electrons of the lone pair of the substituent on the aromatic ring. thing

(Equation 1) (Here, Nπ represents the total number of π electrons, and N _lone is a linear, branched, or cyclic alkoxy group, alkenyloxy group, aryloxy group, aralkyl group having 1 to 12 carbon atoms as the substituent. Represents the total number of electrons in the lone or unshared electron pair of an oxy group or a hydroxyl group, and two or more alkoxy groups or hydroxyl groups may be bonded to each other to form a 5- or more-membered ring structure, provided that benzo is used. (Excluding the dioxol structure, and when Nπ = 6, the substituent does not include a hydroxyl group.)

Alkali-soluble resin (B-3) (B-3) Alkyl etherified, aryl etherified, alkenyl etherified or aralkyl etherified polyvinylphenol in which phenolic hydroxyl groups are partially converted, and phenolic hydroxyl groups are partially Specifically, an alkali-soluble resin containing at least one selected from the group consisting of hydrogenated polyvinyl phenol that has been alkyletherified, aryletherified, alkenyletherified or aralkyletherified.

Hereinafter, the alkali-soluble resins (B-1) to (B-3) will be described in detail. (1) The Present Invention (B-1) Alkali-Soluble Resin In the present invention, the alkali-soluble resin (B-1) has a phenol structure having at least one OH group at a meta position from a site linked to the main chain skeleton of the resin. Containing a repeating unit having a molecular weight distribution of 1.0 to 1.5.
Is an alkali-soluble resin in the range. In a chemically amplified negative resist, a cross-linking agent and an alkali-soluble resin react by an action of an acid catalyst generated by irradiation with actinic rays, radiation, or an electron beam to form a cross-linked structure and become insoluble in an alkali developer. At this time, at least O
When an alkali-soluble resin containing a phenol structure having one H group is used, the molecular weight distribution of the resin is further reduced, and when a resin having a more uniform molecular weight is used, the crosslinking efficiency is specifically improved and sensitivity is improved. Was found to increase. As such a resin, preferably, m-polyvinylphenol resin, a copolymer having a structural unit derived from m-vinylphenol, and a resin obtained by partially protecting or modifying the m-polyvinylphenol resin, A resin such as a (meth) acrylate polymer having a phenol skeleton can be widely used, and a more preferred example is a phenolic resin containing a repeating structural unit represented by the general formula (a).

[0019]

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In the formula, R ₁ represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group, oxyalkyl group or haloalkyl group. x represents an integer of 0 to 3. R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or an acyl group which may have a substituent. R
_{When 2} there are a plurality, the plurality of R ₂ may be the same or different. R ₃ is a hydrogen atom, a halogen atom, a cyano group,
Or an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group which may have a substituent. When R ₃ there are a plurality, the plurality of R ₃ may be the same or different. Further, _two of the plurality of R ₂ , two of the plurality of R ₃ , or R ₂ and R ₃ may be combined to form a ring.

A ₁ may have a single bond or a substituent,
Valent alkylene group, alkenylene group, cycloalkylene group or arylene group, or -O -, - SO ₂ -,
_{-O-CO-R 5 -,} - CO-O-R 6 -, - CO-N
(R ₇ ) represents —R ₈ —. R ₅ , R ₆ and R ₈ may be the same or different and may have a single bond, an ether group, an ester group, an amide group, a urethane group or a ureido group, or may have a substituent. Good represents a divalent alkylene group, alkenylene group, cycloalkylene group, or arylene group. R ₇ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent.

The alkyl group of R _{1 to} R ₃ and R ₇ is preferably an alkyl group having 1 to 8 carbon atoms,
For example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group,
An octyl group can be mentioned. The cycloalkyl groups of R _{2 to} R ₃ and R ₇ may be monocyclic or polycyclic. Preferred examples of the monocyclic type include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group each having 3 to 8 carbon atoms. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, and a tricyclodecanyl group.

The alkenyl group of R _{2 to} R ₃ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group and a cyclohexenyl group. The aryl group of R _{2 to} R ₃ and R ₇ is preferably an aryl group having 6 to 15 carbon atoms, for example, a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, Naphthyl group,
And an anthryl group. R _{2 to} R ₃ , R ₇
The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The oxyalkyl group for R ₁ is preferably an oxyalkyl group having 1 to 4 carbon atoms, for example, an alkoxy group having 1 to 4 carbon atoms such as a hydroxy group, a methoxy group, an ethoxy group and a butoxy group. And an oxymethyl group, an oxyethyl group, an oxypropyl group, and an oxybutyl group substituted by an acyl group having 1 to 4 carbon atoms such as an acetoxy group, a propanoyloxy group and a butanoyloxy group. As the haloalkyl group for R ₁ ,
It is preferably a haloalkyl group having 1 to 4 carbon atoms, and examples thereof include a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, and a bromoethyl group. The acyl group for R ₂ is preferably an acyl group having 1 to 10 carbon atoms, and examples thereof include a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, and a benzoyl group.

The alkylene group for A ₁ , R ₅ , R ₆ and R ₈ is preferably an alkylene group having 1 to 8 carbon atoms,
Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. The alkenylene group preferably has 2 to 2 carbon atoms.
These are six alkenylene groups, for example, an ethenylene group, a propenylene group, a butenylene group and the like.
The cycloalkylene group preferably has 5 to 8 carbon atoms.
Cycloalkylene groups, for example, a cyclopentylene group, a cyclohexylene group and the like. The arylene group is preferably an arylene group having 6 to 12 carbon atoms, for example, a phenylene group, a tolylene group,
Examples include a xylylene group and a naphthylene group.

Further, these groups may further have a substituent. Examples of the substituent include those having active hydrogen such as an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and an alkoxy group. Groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, benzoyloxy group, etc.), Examples include an alkoxycarbonyl group (a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, etc.), a cyano group, a nitro group, and the like.
Particularly, those having active hydrogen such as an amino group, a hydroxyl group and a carboxyl group are preferable.

Further, two of a plurality of R ₂ and a plurality of R ₃
And the ring which may be formed by combining R ₂ and R ₃ may be a ring which may contain a 4- to 7-membered hetero atom (oxygen atom, nitrogen atom, sulfur atom) Specific examples of the formed structure preferably include a benzofuran ring, a benzodioxonol ring, a benzopyran ring, an indole ring, a benzimidazole ring, a benzopyrazole ring, and a benzothiophene ring.

The resin of the present invention (B) may be a resin comprising only the repeating structural unit of the general formula (a), but for the purpose of further improving the performance of the negative resist of the present invention,
Other polymerizable monomers may be copolymerized.

The copolymerizable monomers that can be used include the following. For example, acrylates other than the above, acrylamides, methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, addition polymerizable unsaturated bonds selected from crotonates and the like. It is a compound having one.

Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate) , Chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2
-Dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) aryl acrylate (such as phenyl acrylate);

Methacrylic esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate , Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.),
Aryl methacrylates (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (where the alkyl group has 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl) Group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (aryl group includes, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group,
Examples include a cyanophenyl group, a hydroxyphenyl group, and a carboxyphenyl group. ), N, N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group, etc.), N-diarylacrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like ;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl Group, cyclohexyl group, etc.), N
-Aryl methacrylamide (an aryl group includes a phenyl group and the like), N, N-dialkyl methacrylamide (an alkyl group includes an ethyl group, a propyl group and a butyl group), N, N-diaryl Methacrylamide (an aryl group includes a phenyl group and the like), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide and the like;
Allyl compounds, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol Such;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether,
Ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, Tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-
2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate and vinyl butoxy acetate , Vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-
Phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

Styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene) , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluors Ren, trifluoromethyl styrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), carboxystyrene, vinylnaphthalene;

Crotonic esters, for example, alkyl crotonates (eg, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.) ); Dialkyl esters of maleic acid or fumaric acid (eg,
Dimethyl maleate, dibutyl fumarate, etc.), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile and the like. In addition, generally, any addition-polymerizable unsaturated compound that can be copolymerized may be used.

Among these, monomers having a carboxyl group such as carboxystyrene, N- (carboxyphenyl) acrylamide, N- (carboxyphenyl) methacrylamide, and monomers improving alkali solubility such as maleimide are copolymerization components. Is preferred. The content of the other polymerizable monomer in the resin (B-1) in the invention is preferably 50 mol% or less, more preferably 30 mol% or less, based on all repeating units.

Specific examples of the resin (B-1) having a repeating structural unit represented by the general formula (a) are shown below, but the present invention is not limited thereto.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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In the above specific examples, n represents a positive integer. x,
y and z represent the molar ratio of the resin composition, and x = 30 to 95, y = 5 to 70, and preferably x =
It is used in the range of 50 to 90, y = 10 to 50. In a resin consisting of three components, x = 30 to 90, y = 5 to 65,
z = 5 to 65, preferably x = 50 to 90, y = 5 to 4
5, used in the range of z = 5-45.

The preferred molecular weight of the resin (B-1) in the present invention, preferably the resin (B-1) having a repeating unit represented by the general formula (a), is 1,000 by weight average (polystyrene standard). ~ 50,000, preferably 2,
000-30,000, more preferably 2,500-1
Used in the range of 5,000. Molecular weight distribution (Mw / M
n) is in the range of 1.0 to 1.5, more preferably in the range of 1.0 to 1.2. The smaller the molecular weight distribution, the higher the crosslinking efficiency and the higher the sensitivity. Further, the effect of excellent resolution and pattern edge roughness is exhibited. Here, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) can be obtained by gel permeation chromatography (polystyrene conversion value). The content of the repeating structural unit represented by the general formula (a) in the resin (B-1) is from 5 to 100 mol%, preferably from 50 to 100 mol%, based on all repeating units.
More preferably, it is 70 to 100 mol%.

The resin (B-1) used in the present invention is described in, for example, JP-A-4-195138 and JP-A-4-35065.
7, JP-A-4-350658, JP-A-6-4122
2, each specification of JP-A-6-65333, Poly
m. J. , 18, 1037 (1986), Pol
ym. J. , 22, p. 386 (1990), Mak
romol. Chem. Suppl. , 15 volumes, 167
Page (1989) and the like. That is, the desired alkali-soluble resin can be obtained by a so-called living anion polymerization method. Further, it can also be obtained by combining a resin synthesized by radical polymerization with a soluble good solvent and a poor solvent, and performing molecular weight fractionation or fractionation by gel chromatography. These resins may be used alone or in combination of two or more.

[II] Alkali-soluble resin (B-2) The alkali-soluble resin (B-2) in the present invention is a resin satisfying the following conditions (1) and (2). (1) It has at least one kind of a repeating unit derived from a monomer having an aromatic ring having 6 to 20 carbon atoms and an ethylenically unsaturated group bonded to the aromatic ring directly or via a linking group. (2) The relationship of the formula (I) holds between the number of electrons of the π electron of the aromatic ring and the number of lone pairs of the substituent on the aromatic ring.

[0052]

(Equation 2)

Here, Nπ represents the total number of π electrons.
_lone is the total number of unshared electron pairs of a linear, branched, or cyclic alkoxy, alkenyloxy, aryloxy, aralkyloxy, or hydroxyl group having 1 to 12 carbon atoms as the substituent. Represents Adjacent two of two or more alkoxy groups or hydroxyl groups may be bonded to each other to form a 5- or more-membered ring structure. However, the benzodioxole structure is excluded. When Nπ = 6,
The substituent does not contain a hydroxyl group.

In particular, Nπ + (1/2) N in the formula (I)
_Lone is preferably in the range of 10 to 40 because it has a structure that easily generates secondary electrons. Preferred aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, biphenyl, and the like. Preferred substituents on the aromatic ring include a hydroxyl group, a methoxy group, an ethoxy group, and an isopropyl group. Can be. In the case of an aromatic ring in which the total number of π electrons Nπ is 10 or more (for example, an aromatic ring such as a naphthalene ring, an anthracene ring or a phenanthrene ring, or biphenyl), the substituent on this aromatic ring has an unshared electron pair. No group (N _lone = 0
Which may be, for example, hydrogen and a saturated alkyl group.

More specifically, the alkali-soluble resin (B-2) of the present invention preferably has a repeating unit represented by the following general formulas (1) to (5) as a constituent.

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Embedded image In the general formulas (1) to (5), R ₁₀₁ represents a hydrogen atom or a methyl group. L represents a divalent linking group. Ra,
Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, and Rl each independently represent a linear, branched, or cyclic alkyl group, alkenyl group, or aryl group having 1 to 12 carbon atoms. Represents an aralkyl group or a hydrogen atom. These may be connected to each other to form a 5- or more-membered ring having 24 or less carbon atoms. l, m, n, p, q, r, s, t, u, v, w, x represent integers from 0 to 3, l + m + n = 2,3, p + q + r = 0 , 1,2,3, s + t + u = 0,1,2,
3. Satisfies v + w + x = 0,1,2,3. However, in the general formula (1), Ra, Rb, and Rc are not hydrogen atoms. The general formula (1) excludes a benzodioxole structure.

Examples of Ra, Rb and Rc include hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, cyclohexyl, Octyl, decyl, dodecyl, allyl, benzyl, phenyl, cumyl and the like. Further, examples thereof include those linked to each other to form a methyl-substituted dioxole ring, an ethyl-substituted dioxole ring, a phenyl-substituted dioxole ring, a dimethyl-substituted dioxole ring, and a dioxane ring.

Examples of Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Rl include hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, Examples include a pentyl group, a neopentyl group, a hexyl group, a cyclohexyl group, an octyl group, a decyl group, a dodecyl group, an allyl group, a benzyl group, a phenyl group, and a cumyl group. Rd to Rf, Rg to Ri or Rj to Rl are dioxole rings,
Those forming a methyl-substituted dioxole ring, an ethyl-substituted disoxole ring, a phenyl-substituted dioxole ring, a dimethyl-substituted dioxole ring, or a dioxane ring are also exemplified.

Examples of L include a single bond, -CH ₂ -,-
_{COO -, - COOCH 2 -,} - OCH 2 CH 2 O -, -
OCH ₂ —, —CONH— and the like.

In each aromatic ring represented by Y, the position of a bond bonded to the main chain or the position of a bond bonded to the substituent may be any position on the aromatic ring.

Preferred examples of these structures are shown below, but are not limited thereto.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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In the present invention, the alkali-soluble resin (B
-2) can be synthesized by a known method such as radical polymerization, cationic polymerization, or anionic polymerization. It is easiest to perform radical polymerization by combining corresponding monomers, but depending on the type of monomer, more preferable synthesis can be achieved by using cationic polymerization or anionic polymerization. Further, when the monomer causes a reaction other than polymerization depending on the type of the polymerization initiator, a desired polymer can be obtained by polymerizing a monomer having an appropriate protecting group introduced and deprotecting after polymerization. As for the polymer having alkoxy, a desired polymer can also be obtained by performing an etherification reaction of a hydroxyl group of a polymer having a corresponding hydroxyl group. The polymerization method is described in Experimental Chemistry Course 28 Polymer Synthesis, New Experimental Chemistry Course 19 Polymer Chemistry [I], and the like.

Further, the alkali-soluble resin (B-
2) has a molecular weight of more than 3,000 and 1,000,000
0 or less. Preferably, the weight average molecular weight is 3,000.
It exceeds 0 and is 500,000 or less. More preferably, the weight average molecular weight is more than 3,000 and 100,000
0 or less.

The molecular weight distribution (Mw / Mn) of the alkali-soluble resin (B-2) which can be synthesized by the above synthesis method is as follows:
It is preferably from 1.0 to 1.5, whereby the sensitivity of the resist can be particularly increased. The alkali-soluble resin having such a molecular weight distribution can be synthesized by using living anion polymerization in the above synthesis method. Specific examples of the alkali-soluble resin (B-2) in the invention are shown below.

[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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[0087]

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[0088]

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[0089]

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[0090]

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(3) Alkali-soluble resin (B-3) The alkali-soluble resin (B-3) used in the present invention is:
The phenolic hydroxyl group is partially alkyl etherified,
Aryl etherified, alkenyl etherified or aralkyl etherified polyvinyl phenol, and phenolic hydroxyl groups are partially alkyl etherified,
It contains at least one member selected from the group consisting of aryl-etherified, alkenyl-etherified or aralkyl-etherified hydrogenated polyvinylphenol.

More specifically, the alkali-soluble resin (B-3) of the present invention is preferably a resin represented by the following general formula (1).

[0093]

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In the general formula (1), R represents a linear, branched or cyclic alkyl, aryl, alkenyl or aralkyl group having 1 to 12 carbon atoms.
Specific examples of a methyl group, an ethyl group, a propyl group,
Isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, allyl, benzyl, phenyl, cumyl and the like. .

In the above general formula (1), the ratio of various etherified phenol units (mol) / phenol units (mol) is preferably in the range of 1/99 to 30/70.

Preferred examples of these structures (BP-
1) to (BP-35) are listed below, but are not limited thereto.

[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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In the present invention, the alkali-soluble resin (B
-3) can be synthesized by a known method such as radical polymerization, cationic polymerization, or anionic polymerization. It is easiest to perform radical polymerization by combining corresponding monomers, but depending on the type of monomer, more preferable synthesis can be achieved by using cationic polymerization or anionic polymerization. Further, when the monomer causes a reaction other than polymerization depending on the type of the polymerization initiator, a desired polymer can be obtained by polymerizing a monomer having an appropriate protecting group introduced and deprotecting after polymerization. As for the polymer having alkoxy, a desired polymer can also be obtained by performing an etherification reaction of a hydroxyl group of a polymer having a corresponding hydroxyl group. The polymerization method is described in Experimental Chemistry Course 28 Polymer Synthesis, New Experimental Chemistry Course 19 Polymer Chemistry [I], and the like.

Further, the alkali-soluble resin (B-
The weight average molecular weight of 3) exceeds 3,000, and
It is preferably not more than 000, more preferably more than 3,000 and not more than 500,000, further preferably more than 3,000 and not more than 100,000.

The molecular weight distribution (Mw / Mn) of the alkali-soluble resin (B-3) which can be synthesized by the above synthesis method is as follows:
It is preferably from 1.0 to 1.5, whereby the sensitivity of the resist can be particularly increased. The alkali-soluble resin having such a molecular weight distribution can be synthesized by using living anion polymerization in the above synthesis method. The amount of the resin (B) added is 30 to 95% by weight, preferably 4% by weight, based on the total solid content of the composition.
It is used in the range of 0 to 90% by weight, more preferably 50 to 80% by weight.

[2] Compound of the present invention (A) capable of generating an acid upon irradiation with an electron beam or X-ray having a disulfone group The compound of (A) which can be used in the present invention has a disulfone group, A compound that decomposes upon irradiation with an electron beam or X-ray to generate an acid. As the compound of (A),
Disulfone derivatives represented by the following general formula (PAG) are preferred.

Ra—SO ₂ —SO ₂ —Rb General formula (PAG) In the formula, Ra and Rb are each independently substituted or unsubstituted,
Represents an aryl group, an alkyl group, a cycloalkyl group or an aralkyl group.

Here, the aryl group has 6 to 6 carbon atoms.
There are 15 aryl groups, such as a phenyl group, a tolyl group, a naphthyl group, and an anthryl group. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-
Examples thereof include an ethylhexyl group and an octyl group.
The cycloalkyl group may be monocyclic or polycyclic.
Preferred examples of the monocyclic type include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group each having 3 to 8 carbon atoms. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, and a tricyclodecanyl group. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Examples of the substituent of the aryl group, alkyl group, cycloalkyl group or aralkyl group include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an oxyalkyl group, a haloalkyl group and an acyl group. be able to. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl Groups can be mentioned. The cycloalkyl group may be monocyclic or polycyclic. Preferred examples of the monocyclic type include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group each having 3 to 8 carbon atoms. Examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-
A pinel group, a tricyclodecanyl group and the like can be preferably mentioned.

The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group and a cyclohexenyl group. The aralkyl group preferably has 7 carbon atoms.
~ 12 aralkyl groups, for example, benzyl group,
Examples include a phenethyl group and a naphthylmethyl group.

The oxyalkyl group is preferably an oxyalkyl group having 1 to 4 carbon atoms, for example, an alkoxy group having 1 to 4 carbon atoms such as a hydroxy group, a methoxy group, an ethoxy group and a butoxy group, or an acetoxy group. Group, a propanoyloxy group, a butanoyloxy group, etc.
Examples thereof include an oxymethyl group, an oxyethyl group, an oxypropyl group, and an oxybutyl group substituted with 4 to 4 acyl groups. The haloalkyl group is preferably a haloalkyl group having 1 to 4 carbon atoms, and examples thereof include a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, and a bromoethyl group. The acyl group preferably has 1 to 1 carbon atoms.
There are 10 acyl groups, for example, formyl group, acetyl group, propanoyl group, butanoyl group, pivaloyl group, benzoyl group and the like. Specific examples include the following compounds, but are not limited thereto.

[0114]

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[0115]

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[0116]

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In the present invention, other than the above, other acid generators may be used in combination. Examples of such acid generators that can be used in combination include known photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and microresists. Light (400
-200 nm ultraviolet light, far ultraviolet light, particularly preferably g
Line, h line, i line, KrF excimer laser light), ArF
A compound capable of generating an acid by an excimer laser beam, an electron beam, an X-ray, a molecular beam or an ion beam, and a mixture thereof can be appropriately selected and used in combination.

Other compounds that generate an acid upon irradiation with an electron beam or X-ray used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng., 18,
387 (1974), TS Bal et al, Polymer, 21, 423 (1980)
Etc., diazonium salts, U.S. Pat.No. 4,069,055,
4,069,056, Re 27,992, ammonium salt described in JP-A-3-140140, etc., DC Necker et al, Macrom
olecules, 17, 2468 (1984), CS Wen et al, Teh, Pr.
oc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988),
U.S. Pat.No.4,069,055, phosphonium salts described in 4,069,056 and the like, JV Crivello et al, Macromorecules,
10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31
(1988), European Patent Nos. 104,143, 339,049, 410,
No. 201, JP-A-2-150848, Iodonium salts described in JP-A-2-29514, etc., JV Crivello et al, Polymer J.
17, 73 (1985), JV Crivello et al., J. Org.
m., 43, 3055 (1978), WR Watt et al, J. Polymer S
ci., Polymer Chem. Ed., 22, 1789 (1984), JV Criv
ello et al, Polymer Bull., 14, 279 (1985), JV Cr
ivello et al, Macromorecules, 14 (5), 1141 (1981),
JV Crivelloet al, J. Polymer Sci., Polymer Che
m. Ed., 17, 2877 (1979), European Patent Nos. 370,693, 16
No. 1,811, No. 410,201, No. 339,049, No. 233,567, No.
Nos. 297,443 and 297,442; U.S. Pat.No. 4,933,377;
3,902,114, 4,760,013, 4,734,444, 2,832
No. 3,827, Dokoku Patent No. 2,904,626, No. 3,604,580,
3,604,581, etc., sulfonium salts, JV Crivell
o et al, Macromorecules, 10 (6), 1307 (1977), JV
Crivello et al, J. Polymer Sci., Polymer Chem. E
d., 17, 1047 (1979), etc., selenonium salts, CS
Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478
Onium salts such as arsonium salts described in Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60 -239736
No., JP-A-61-169835, JP-A-61-169837, JP-A-62
-58241, JP-A-62-212401, JP-A-63-70243, and organic halogen compounds described in JP-A-63-298339, K. Me
ier et al, J. Rad.Curing, 13 (4), 26 (1986), TP
Gill et al, Inorg. Chem., 19, 3007 (1980), D. Astru
c, Acc.Chem.Res., 19 (12), 377 (1896), JP-A-2-614
Organometallics / organic halides described in No. 45, etc., S. Hayas
e et al, J. Polymer Sci., 25, 753 (1987), E. Reichm
anis et al, J. Pholymer Sci., Polymer Chem. Ed., 2
3, 1 (1985), QQ Zhuetal, J. Photochem., 36, 85,
39, 317 (1987), B. Amit et al, Tetrahedron Lett., (2
4) 2205 (1973), DHR Barton et al, J. Chem Soc.,
3571 (1965), PM Collins et al, J. Chem. Soc., Pe
rkin I, 1695 (1975), M. Rudinstein et al, Tetrahedro
n Lett., (17), 1445 (1975), JW Walker et al, J.
Am. Chem. Soc., 110, 7170 (1988), SC Busman et a
l, J. Imaging Technol., 11 (4), 191 (1985), HM Hou
lihan et al, Macormolecules, 21, 2001 (1988), p.
M. Collins et al, J. Chem. Soc., Chem. Commun., 532
(1972), S. Hayase et al, Macromolecules, 18, 1799
(1985), E. Reichmanis et al, J. Electrochem. Soc.,
Solid State Sci. Technol., 130 (6), FM Houlihan
et al, Macromolcules, 21, 2001 (1988), European Patent No. 0
290,750, 046,083, 156,535, 271,851,
No. 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531
JP-A-60-198538, JP-A-53-133022 and the like, a photoacid generator having a 0-nitrobenzyl-type protecting group, M.TU
NOOKA et al, Polymer Preprints Japan, 35 (8), G. Be
rner et al, J. Rad. Curing, 13 (4), WJ Mijs et
al, Coating Technol., 55 (697), 45 (1983), Akzo, H.
Adachi et al, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 044,115, 618,
No. 564, No. 0101,122, U.S. Pat.Nos. 4,371,605, 4,43
No. 1,774, JP-A-64-18143, JP-A-2-245756, and compounds that generate sulfonic acid upon photodecomposition represented by iminosulfonate described in JP-A-3-140109 and the like. it can.

Further, a compound in which an acid or a group capable of generating an acid upon irradiation with an electron beam or X-ray is introduced into a main chain or a side chain of a polymer, for example, ME Woodhouse
et al, J. Am. Chem. Soc., 104, 5586 (1982), SP P.
appas et al, J. Imaging Sci., 30 (5), 218 (1986), S.
Kondo et al, Makromol. Chem., Rapid Commun., 9,62
5 (1988), Y. Yamada et al, Makromol. Chem., 152, 15
3, 163 (1972), JVCrivello et al, J. Polymer Sc
i., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
No. 3,849,137, Dokoku Patent No. 3914407, JP-A-63-26653,
JP-A-55-164824, JP-A-62-69263, JP-A-63-1460
No. 38, JP-A-63-163452, JP-A-62-153853, JP-A
Compounds described in JP-A-63-146029 can be used.

Further, VNR Pillai, Synthesis, (1),
1 (1980), A. Abad et al, Tetrahedron Lett., (47) 45
55 (1971), DHR Barton et al, J. Chem. Soc.,
(C), 329 (1970), U.S. Patent 3,779,778, European Patent 1
Compounds that generate an acid by light described in No. 26,712 and the like can also be used.

Among the compounds capable of generating an acid upon being decomposed by irradiation with an electron beam or X-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).

[0122]

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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
Is shown. Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0124]

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[0125]

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[0126]

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

[0128]

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[0129] Here, the formula Ar ^1, Ar ² represents independently, 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 for the aryl group include an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, a nitro group, a carboxyl group, a mercapto group, a hydroxy group and a halogen atom. And an alkyl group includes an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

[0131] Z ^- is an anion, in particular which may have a substituent alkyl sulfonate, cycloalkyl sulfonate, perfluoroalkyl sulfonic acids, have a arylsulfonic acid (e.g., substituent And anions such as benzenesulfonic acid, naphthalenesulfonic acid, and anthracenesulfonic acid.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

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

[0134]

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[0135]

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[0136]

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[0137]

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[0138]

[Of 60]

[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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The above-mentioned onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knapcz
yk et al, J. Am. Chem. Soc., 91, 145 (1969), AL
Maycok et al, J. Org.Chem., 35, 2532, (1970), E.
Goethas et al, Bull.Soc.Chem.Belg., 73, 546, (196
4), HM Leicester, J. Ame. Chem. Soc., 51, 3587.
(1929), JV Crivello et al, J. Polym. Chem. Ed.,
18, 2677 (1980), U.S. Pat.Nos. 2,807,648 and 4,247,
No. 473, JP-A-53-101331 and the like. (3) An iminosulfonate derivative represented by the following general formula (PAG6).

[0145]

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In the formula, R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.
Specific examples include the following compounds, but are not limited thereto.

[0147]

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[0148]

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[0149]

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[0150]

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(4) A diazodisulfone derivative represented by the following general formula (PAG7).

[0152]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0154]

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The amount of the compound capable of generating an acid upon irradiation with an electron beam or X-ray having a disulfone group of the present invention (B) is 0.1 to 0.1% based on the total solid content of the composition of the present invention.
-20% by weight, preferably 0.5-10% by weight, more preferably 1-7% by weight. These compounds may be used alone or in combination of two or more. The amount of addition of the compound having a disulfone group of the present invention (B) other than a compound capable of generating an acid upon irradiation with an electron beam or X-ray is usually 0 based on the total solid content of the resist composition.
-10% by weight, preferably 0.1-5% by weight, more preferably 0.5-3% by weight.

[3] Acid Crosslinking Agent of the Present Invention (C) In the present invention, together with an alkali-soluble resin and an acid generator, an acid generated from the compound (A) by irradiation with an electron beam or X-ray is used to form (B) )) (Hereinafter referred to as an acid crosslinking agent or simply as a crosslinking agent, as appropriate). Here, a known acid crosslinking agent can be effectively used. Preferably, it is a compound or resin having one or more, more preferably 2 to 16, more preferably 4 to 10 hydroxymethyl, alkoxymethyl, acyloxymethyl or alkoxymethyl ether groups, or an epoxy compound. .

More preferably, alkoxymethylated, acyloxymethylated melamine compounds or resins, alkoxymethylated, acyloxymethylated urea compounds or resins, hydroxymethylated, alkoxymethylated, acyloxymethylated phenol compounds or resins, and alkoxymethylated Examples include etherified phenol compounds and resins.

(I) As the phenol compound,
Preferably, it has a molecular weight of 1200 or less, contains 3 to 5 benzene rings in the molecule, further has two or more hydroxymethyl groups or alkoxymethyl groups in total, and has at least one of the hydroxymethyl group and the alkoxymethyl group. Phenol derivatives formed by concentrating on a benzene ring or binding by sorting. By using such a phenol derivative, the effects of the present invention can be made more remarkable. The alkoxymethyl group bonded to the benzene ring preferably has 6 or less carbon atoms. Specifically, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group,
A sec-butoxymethyl group and a t-butoxymethyl group are preferred. Further, an alkoxy-substituted alkoxy group such as a 2-methoxyethoxy group and a 2-methoxy-1-propyl group is also preferable. Among these phenol derivatives, particularly preferred ones are listed below.

[0159]

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[0160]

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[0161]

[Of 75]

[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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(Wherein L ^{1 to} L ⁸ may be the same or different and each represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group.) A phenol derivative having a hydroxymethyl group corresponds to By reacting a phenol compound having no hydroxymethyl group (compound where L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. At this time, the reaction is preferably performed at a reaction temperature of 60 ° C. or lower in order to prevent resinification and gelation. Specifically, JP-A-6-282067 and JP-A-7-64
No. 285, for example.

A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, the reaction is preferably performed at a reaction temperature of 100 ° C. or less in order to prevent resinification and gelation. Specifically, it can be synthesized by a method described in European Patent EP632003A1 or the like. A phenol derivative having a hydroxymethyl group or an alkoxymethyl group synthesized in this manner is preferable in terms of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage.
Such a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in total and concentrated on one of the benzene rings or bonded by distribution may be used alone. A combination of the above may be used.

(Ii) N-hydroxymethyl group, N-
As the compound having an alkoxymethyl group or an N-acyloxymethyl group, European Patent Publication (hereinafter referred to as “E
No. 0,133,216, West German Patent Nos. 3,634,671 and 3,711,264, and monomer-oligomer-melamine-formaldehyde condensates; Examples include urea-formaldehyde condensate, and benzoguanamine-formaldehyde condensate disclosed in the alkoxy-substituted compound disclosed in EP-A-0,212,482. More preferred examples include, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups, or N-acyloxymethyl groups, among which N-alkoxymethyl derivatives are particularly preferred. .

(Iii) Examples of the epoxy compound include monomer, dimer, oligomer, and polymer epoxy compounds containing one or more epoxy groups. For example, a reaction product of bisphenol A with epichlorohydrin, a reaction product of a low molecular weight phenol-formaldehyde resin with epichlorohydrin and the like can be mentioned. In addition, US Pat. No. 4,026,705,
Epoxy resins described and used in British Patent No. 1,539,192 can be mentioned.

The crosslinking agent is used in an amount of generally 3 to 65% by weight, preferably 5 to 50% by weight, based on the total solid content of the resist composition. If the amount of the cross-linking agent is less than 3% by weight, the residual film ratio decreases, and if it exceeds 65% by weight, the resolving power decreases, and the stability of the resist solution during storage is not so preferable.

In the present invention, the above-mentioned (i) phenol compound and, for example, the above-mentioned other crosslinking agent (ii),
(Iii) can be used in combination. The ratio of other crosslinking agents that can be used in combination with the phenol derivative is from 100/0 to 20/80, preferably from 90/10 to 4 in a molar ratio.
0/60, more preferably 80/20 to 50/50.

[4] Other components that may be used in the composition of the present invention The negative resist composition of the present invention may further contain, if necessary, an organic basic compound, a dye, a surfactant and the like. be able to.

[4] -1 Organic Basic Compound Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0175]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and include a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, Represents 6 to 6 hydroxyalkyl groups or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R
²⁵¹ and R ²⁵² may combine with each other to form a ring. R
²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and represent an alkyl group having 1 to 6 carbon atoms. Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred are both substituted or unsubstituted amino groups and ring structures containing nitrogen atoms. 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 indazole, imidazole, 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, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

As particularly preferred compounds, guanidine and
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-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, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, and the like, but are not limited thereto. These nitrogen-containing basic compounds are used alone or in combination of two or more.

The ratio of the acid generator and the organic basic compound used in the composition is preferably (acid generator) / (organic basic compound) (molar ratio) = 2.5 to 300. When the molar ratio is less than 2.5, the sensitivity becomes low and the resolving power may decrease. On the other hand, when the molar ratio exceeds 300, the thickness of the resist pattern increases over time until the heat treatment after exposure, and the resolving power may decrease. . (Acid generator) / (organic basic compound) (molar ratio) is preferably from 5.0 to 200, more preferably from 7.0 to 150.

[4] -2 Dye Suitable dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 1
03, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-5
05 (all manufactured by Orient Chemical Industries, Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170)
B), malachite green (CI42000), methylene blue (CI52015) and the like.

[4] -3 Surfactants Surfactants can be added to the above solvents. 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 Te - door,

Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate; EFTOP EF301 and EF3
03, EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florade FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-
382, SC101, SC102, SC103, SC1
04, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), fluorinated or silicon-based surfactants such as Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Acrylic or methacrylic (co) polymerized polyflow N
o. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK)
And the like. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

The composition of the present invention is dissolved in a solvent capable of dissolving each of the above components, and applied 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 mixed to use.

In the manufacture of precision integrated circuit devices, the pattern formation step on a resist film is performed by forming a negative (the negative) of the present invention on a substrate (eg, a silicon / silicon dioxide cover, a glass substrate, a transparent substrate such as an ITO substrate, etc.). A good photoresist pattern is formed by applying a photoresist composition and then irradiating with an electron beam (under an acceleration voltage of 75 keV or more) or using an X-ray lithography apparatus, heating, developing, rinsing and drying. can do.

Examples of the developer for the negative photoresist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; ethylamine;
primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, Aqueous solutions of alkalis such as quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperidine can be used. Further, an appropriate amount of an alcohol such as isopropyl alcohol or a surfactant such as a nonionic surfactant may be added to an aqueous solution of the above alkalis. Of these developers, quaternary ammonium salts are preferred, and tetramethylammonium hydroxide and choline are more preferred.

[0187]

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.

(1) Synthesis of Alkali-Soluble Resin (B-1) [Synthesis Example 1 (Synthesis of Example (1) of Resin (B-1)]]
After adding 0.004 mol of butyllithium and cooling to −78 ° C., a solution of 35 g (0.20 mol) of 3-t-butoxystyrene, also cooled to −78 ° C., in 20 ml of tetrahydrofuran was added and stirred for 1 hour. . Thereafter, 10 ml of methanol was added to the reaction solution to stop the polymerization reaction. The resulting reaction solution was poured into methanol with stirring to precipitate a white resin. The precipitated resin was filtered and dried, and then dissolved in acetone (300 ml).
% Hydrochloric acid was added, and the mixture was heated and stirred at 60 ° C. for 8 hours. Thereafter, the mixture was poured into 2 L of ion-exchanged water with stirring to precipitate a white resin. After washing with deionized water and drying under reduced pressure, 19.2 g of the resin (B-1) of the present invention (Example 1) was obtained. NMR measurement confirmed that the structure of the resin was (B-1) Example (1).
When the molecular weight was measured at C, the weight average (Mw: in terms of polystyrene) was 5,100, and the molecular weight distribution (Mw / M
n) was 1.1.

Synthesis Example 2 (Synthesis of Example (19) of Resin (B-1)) In place of 35 g of 3-t-butoxystyrene in Synthesis Example 1, 24.7 g of 3-t-butoxystyrene (0.
14 mol) and 10.6 g of 4-t-butoxystyrene
(0.06 mol), and 18.6 g of Resin (B-1) Example (19) of the present invention was synthesized in the same manner as in Synthesis Example 1 except for the above. By NMR measurement, it was confirmed that the structure of the resin was (B-1) Example (19), and when the molecular weight was measured by GPC, the weight average (Mw: converted to polystyrene) was obtained.
Was 4,900, and the molecular weight distribution (Mw / Mn) was 1.1.

[Synthesis Example 3 (Synthesis of Example (24) of Resin (B-1)]] In place of 35 g of 3-t-butoxystyrene in Synthesis Example 1, 30 g of 3-t-butoxystyrene (0.17 g) was used.
Mol) and 4.9 g of 3,4-dimethoxystyrene (0.0 g).
19.6 g of Resin (B-1) Example (24) of the present invention was synthesized in the same manner as in Synthesis Example 1 except for using 3 mol).
According to NMR measurement, the structure of the resin was (B-1) Example (24).
And the molecular weight was measured by GPC. The weight average (Mw: in terms of polystyrene) was 4,5.
The molecular weight distribution (Mw / Mn) was 1.2.

Synthesis Example 4 (Synthesis of Example (35) of Resin (B-1)) 30 g (0.17 mol) of 3-t-butoxystyrene, 4.6 g (0.03 mol) of 1-vinylnaphthalene, Polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd .; trade name V)
-65) 50 mg of 1-methoxy-2-propanol 8
0 ml, and added dropwise to 20 ml of 1-methoxy-2-propanol heated to 70 ° C. over 2 hours under a nitrogen stream and stirring. After 2 hours, 50 mg of an initiator was added, and the reaction was further performed for 2 hours. Thereafter, the temperature was raised to 90 ° C. and stirring was continued for 1 hour.
Continued for hours. After allowing the reaction solution to cool, it was poured into 1 L of ion exchanged water with vigorous stirring to precipitate a white resin. After filtering and drying the obtained resin, acetone 300 m
Then, 3 ml of 36% hydrochloric acid was added, and the mixture was heated and stirred at 60 ° C. for 8 hours. Thereafter, the mixture was poured into 2 L of ion-exchanged water with stirring to precipitate a white resin. Washing with ion-exchanged water, drying under reduced pressure, dissolving in methanol and reprecipitating in hexane were repeated twice to obtain 15.8 g of the resin (B-1) (35) of the present invention. NM
By R measurement, it was confirmed that the structure of the resin was (B-1) Example (35), and when the molecular weight was measured by GPC, the weight average (Mw: in terms of polystyrene) was 6,80.
0 and the molecular weight distribution (Mw / Mn) was 1.3. Hereinafter, the resin (B-1) of the present invention was synthesized in the same manner.

(2) Synthesis of alkali-soluble resin (B-2) (2-1) 16.4 g of 3,4-dimethoxystyrene
(0.1 mol), 4-t-butoxystyrene 158.
7 g (0.9 mol) was dissolved in dry THF and heated to 70 ° C. under a nitrogen stream to obtain an azo radical initiator V manufactured by Wako Pure Chemical Industries, Ltd.
-601 was added at 2% of the total number of moles of the monomer. After reacting for 8 hours, the reaction solution was diluted with THF, precipitated in hexane, purified, and the polymer was taken out. It was decomposed with an acid by a conventional method to obtain Resin (B-2) Example (P-1). G
The weight average molecular weight (Mw) and the molecular weight dispersity (Mw / Mn) were determined by PC measurement. (2-2) A method similar to the above, and using a protected monomer (eg, 4-benzyloxystyrene) to obtain BF _3.
Resin by properly using the cationic polymerization by EtO ₂ (B-
2) Examples of (P-1 ′), (P-1 ″), (P−
2) to (P-51) were synthesized. (2-3) 3,64-dimethoxystyrene 1.64 g
(0.01 mol), 4-t-butoxystyrene 15.
9 g (0.09 mol) was dissolved in dry THF, and the reaction was started by breaking the glass seal using 1 mmol of s-butyllithium at −78 ° C. in a sealed tube. The powder was precipitated in a large amount of hexane and collected and purified. The resin was treated with an acid according to a conventional method to obtain a resin (B-2) example (P-1 ′ ″).

(3) Synthesis of alkali-soluble resin (B-3) (3-1) 4-t-butoxystyrene / 15 g was added to dry THF 27 g, and the mixture was heated to 70 ° C. under a nitrogen stream. When the reaction temperature became stable, an azo radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added in an amount of 2 mol% of the monomer, and the reaction was started. After reacting for 3 hours, 2 mol% of V-601 was added again, and the reaction was further conducted for 3 hours.
The reaction mixture was diluted with THF, poured into a large amount of methanol and precipitated. The obtained polymer is decomposed in a hydrochloric acid acidic solution by a conventional method, precipitated in hexane, and reprecipitated and purified twice.
3) Example (BP-1) was obtained. The molecular weight (Mw: in terms of polystyrene) and the molecular weight dispersity (Mw / Mn) were determined by THF solvent GPC measurement. (3-2) Polyhydroxystyrene (VP manufactured by Nippon Soda)
-8000) was dissolved in 80 ml of NMP. 0.017 mol of potassium carbonate and methyl iodide were added, and the mixture was stirred at 40 ° C for 4 hours. Acetic acid, 0.017 mol, was added and poured into water. Extraction with ethyl acetate and drying gave Resin (B-3) Example (BP-1 '). Other resins (B-
3) Each example was synthesized in the same manner.

Synthesis of Crosslinking Agent [HM-1] 20 g of 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene (Honshu Chemical Industry Co., Ltd. T
risp-PA) was added to a 10% aqueous potassium hydroxide solution, and the mixture was stirred and dissolved. Then, while stirring this solution, 3
60 ml of a 7% aqueous formalin solution was gradually added at room temperature over 1 hour. After stirring at room temperature for 6 hours, the mixture was thrown into a dilute sulfuric acid aqueous solution. The precipitate was filtered, washed sufficiently with water, and recrystallized from 30 ml of methanol to obtain 20 g of a white powder of a phenol derivative having a hydroxymethyl group [HM-1] having the following structure. The purity was 92% (liquid chromatography method).

[0195]

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Synthesis of Crosslinking Agent [MM-1] 20 g of the phenol derivative having a hydroxymethyl group [HM-1] obtained in the above Synthesis Example was added to 1 liter of methanol, and the mixture was heated and stirred to dissolve. Next, 1 ml of concentrated sulfuric acid was added to this solution, and the mixture was heated under reflux for 12 hours. After the completion of the reaction, the reaction solution was cooled, and 2 g of potassium carbonate was added. After sufficiently concentrating this mixture, 300 ml of ethyl acetate was added. This solution was washed with water and concentrated to dryness to obtain 22 g of a white solid of a phenol derivative having a methoxymethyl group [MM-1] having the following structure. 90 purity
% (Liquid chromatography method).

[0197]

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Further, the following phenol derivatives were synthesized in the same manner.

[0199]

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Examples 1 to 14 and Comparative Examples 1 to 3 (1) Application of Resist The components shown in Table 1 below were dissolved in 6.8 g of propylene glycol monomethyl ether acetate / 1.7 g of propylene glycol monomethyl ether. And 0.003 g of triphenylimidazole and Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) as a surfactant.
001 g was added to prepare the resist composition of the present invention.

Each of the sample solutions was filtered through a 0.1 μm Teflon (registered trademark) filter, and then applied to a hexamethyldisilazane-treated silicon wafer by a spin coater. By heating and drying on a plate, a resist film having a thickness of 0.3 μm was obtained.

[0202]

[Table 1]

In Table 1, resins (19), (20), (24) and (25)
The composition (molar ratio) and molecular weight of are as follows. The resins (a) and (b) used in the comparative examples are as follows. (19): x / y = 70/30, Mw = 4,900, Mw / Mn = 1.1 (20): x / y = 85/15, Mw = 5,800, Mw / Mn = 1.1 (24): x / y = 85/15, Mw = 4,500, Mw / Mn = 1.2 (25): x / y = 85/15, Mw = 5,200, Mw / Mn = 1.2 Comparative resin (a): poly (3-hydroxystyrene) (structure example (1)), Mw: 9,700, Mw / Mn = 1.8 Comparative resin (b): poly (4-hydroxystyrene) ), Mw: 5,900, Mw / Mn = 1.1

The ratio in the case of using two kinds of acid generators in Table 1 is a weight ratio. In addition, crosslinking agents CL-1, CL-2
Is:

[0205]

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(2) Formation of resist pattern An electron beam lithography system (acceleration 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 pattern was observed with a scanning electron microscope. The sensitivity is 0.2
The sensitivity was defined as the minimum irradiation energy when resolving a 0 μm line (line: space = 1: 1), and the limit resolution (line and space separated and resolved) at that dose was defined as the resolution. 0.20 μm line (line: space = 1:
For those which did not resolve 1), the limiting resolution was defined as the resolution, and the irradiation energy at that time was defined as the sensitivity. Table 2 shows the performance evaluation results.

[0207]

[Table 2]

From the results shown in Table 2, it can be seen that the negative resist composition in which the composition of the present invention is combined has higher sensitivity and better resolution and profile than the comparative example.

[Examples 15 to 19 and Comparative Example 4] Using the compositions of Examples 2, 5, 7, 8, and 12 and Comparative Example 3,
100K for the resist film created in the same manner as above
Irradiation was performed using an electron beam lithography apparatus under the condition of an acceleration voltage of eV. After irradiation, heating, development, and rinsing were performed in the same manner as in the above example, and the obtained pattern was observed with a scanning electron microscope. Table 3 shows the results of evaluation in the same manner as in the above example.
It was shown to.

[0210]

[Table 3]

From the results shown in Table 3, it can be seen that the negative resist composition of the present invention shows good sensitivity and resolution to the composition of Comparative Example 3 even when irradiated with an electron beam at a high accelerating voltage.

[0212]

According to the negative resist composition for an electron beam and an X-ray of the present invention, sensitivity and sensitivity can be improved even under high accelerating voltage conditions.
A negative resist composition having excellent resolution and a rectangular profile can be provided.

Claims (3)

[Claims] 1. A compound having a disulfone group, which generates an acid upon irradiation with an electron beam or X-ray, (B) a resin which is insoluble in water and soluble in an aqueous alkali solution, and A negative resist composition for electron beam or X-ray, comprising: a crosslinking agent which forms a crosslink with the resin (B). 2. The compound (A) having a disulfone group,
The negative resist composition for electron beam or X-ray according to claim 1, which is a compound represented by the following general formula (PAG). Ra-SO ₂ -SO ₂ -Rb formula (PAG) wherein, Ra, Rb substituted or unsubstituted are each independently
Represents an aryl group, an alkyl group, a cycloalkyl group or an aralkyl group. 3. The electron beam or X according to claim 1, further comprising (D) an organic basic compound.
Negative resist composition for lines.