JP2002174894A - Positive type resist composition for electron beam or x- ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type resist composition for electron beams or X-rays which aims at the improvement of performance in the microfabrication of a semiconductor device using electron beams or X-rays and satisfies sensitivity, resolution and resist shape when electron beams or X-rays are used and to provide a positive type resist composition for electron beams or X-rays having high sensitivity and adaptable to an advanced EB irradiation equipment (an EB block irradiator or an EB stepper (stepwise reduced projection irradiator)) which aims at the enhancement of throughput) having a high accelerating voltage and fit for the mass production of semiconductor devices. SOLUTION: Each of the positive type resist compositions contains a resin having repeating units each having a group capable of generating a specified acid and a low molecular dissolution inhibiting compound having a molecular weight of <=3,000 and decomposable by 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 positive resist composition suitable for use in microlithography processes such as the production of VLSI and high-capacity microchips, and other photofabrication processes. More specifically, the present invention relates to a positive resist composition capable of forming a high-definition pattern using an electron beam, an X-ray, or the like, and is particularly suitable for fine processing of a semiconductor device using a high energy beam such as an electron beam. The present invention relates to a high-sensitivity positive resist composition which can be used for a resist.

[0002]

2. Description of the Related Art The degree of integration of integrated circuits has been increasing, and in the manufacture of semiconductor substrates such as ultra LSIs, it has become necessary to process ultrafine patterns having a line width of less than quarter micron. Was. In order to meet the need, the light source wavelength of an exposure apparatus used for lithography has been increasingly shortened. At present, KrF excimer laser light (248 nm) and ArF excimer laser light (193
nm), and further research is being conducted on the use of F ₂ excimer laser light (157 nm). On the other hand, formation of fine patterns using high energy rays such as electron beams, X-rays, and EUV (13 nm) has been studied. In particular, electron beams and X-rays are positioned as a pattern formation technology for the next generation and beyond, and development of a positive resist capable of forming a rectangular profile with high sensitivity, high resolution, and the like is desired.

In electron beam lithography, an accelerated electron beam gives energy to a compound in a process of colliding with atoms constituting a resist material to cause a reaction of the resist material to form an image. Generally, in the case of an electron beam resist, incident electrons have electric charges and interact with nuclei and electrons of a substance constituting the resist material, so that when an electron beam enters the resist film, scattering occurs (electron For scattering, see “THOMPSON, WILLSON, BOWDEN
Author “Introduction to Microlithography” ACS Symposiu
m Series 219, p. 47-63 "). Therefore, in the irradiated part, the irradiated part spreads from the resist film surface toward the substrate interface, and in the case of a positive resist, there are problems such as formation of a reverse tapered pattern profile and deterioration of resolution. By accelerating the electron beam, the straightness increases, and when the effect of electron scattering is reduced, a high-resolution rectangular pattern can be formed.On the other hand, the permeability of the electron beam to the resist film increases. However, there is a problem that the sensitivity is lowered. As described above, in electron beam lithography, sensitivity, resolution, and resist shape are in a trade-off relationship, and it has been an issue how to make these compatible.

As a resist material for these, a chemically amplified resist mainly utilizing an acid catalysis reaction is used for the purpose of improving sensitivity, and an alkali-soluble group is acid-decomposed as a main component for a positive resist. A chemically amplified composition comprising a resin protected by a functional group and an acid generator has been effectively used.

[0005] Such resins protected with acid-decomposable groups include, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-2229242,
JP-A-63-27829, JP-A-63-36240
Gazette, JP-A-63-250542, Polym.Eng.Sc
i., 23, 12 (1983); ACS. Sym. 242, 11 (1984);
Semiconductor World 1987, November Publication, page 91: Macr
omolecules, 21: 1475 (1988); SPIE, 920: 42
(1988) and the like, a compound capable of generating an acid upon exposure to light and a tertiary or secondary carbon (for example, tert-butyl, 2-
(Cyclohexenyl) in combination with an ester or carbonate compound.

JP-A-2-198747 discloses a photoresist composition containing a resin in which the phenolic hydroxyl group of poly (p-hydroxystyrene) is completely or partially protected by a tetrahydropyranyl group. Is disclosed. Japanese Patent Application Laid-Open No. 219957/1992 also discloses a photoresist composition characterized by containing a resin in which 20 to 70% of the phenolic hydroxyl groups of poly (p-hydroxystyrene) are substituted with acetal groups. Have been. Further, JP-A-5-249
No. 682 also discloses a photoresist composition using a similar acetal-protected resin.

JP-A-8-123032 discloses a photoresist composition using a terpolymer containing a group substituted with an acetal group. Further, Japanese Patent Application Laid-Open
-113667, JP-A-6-266112, JP-A-6-289608, JP-A-7-209
No. 868 discloses a photoresist composition comprising a hydroxystyrene and a (meth) acrylate copolymer.

Further, JP-A-3-249654 discloses a chemically amplified photoresist composition using a polymer of p-tert-butoxycarbonyloxystyrene, and US Pat. No. 4,491,628 discloses an acid generator. Discloses a resist composition using an onium salt.

Further, a compound comprising a mixture of polyhydroxystyrene substituted with a tert-butoxycarbonyloxy group and polyhydroxystyrene substituted with an acetal group as a resin component, a compound capable of generating an acid upon irradiation with radiation, and an organic carboxylic acid JP-A-8-262721, JP-A-9-6002, and JP-A-9-22117 disclose a positive resist composition containing a compound and a polyhydroxystyrene substituted with a tert-butoxycarbonyloxy group and an acetal group. Japanese Patent Application Laid-Open No. 9-6001 discloses a positive resist containing, as a resin component, a mixture with a polyhydroxystyrene substituted with a compound containing an acid-generating compound, an organic carboxylic acid compound and an amine component. I have.

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.

However, in any combination of these compounds, it is difficult to obtain a sufficiently high sensitivity by electron beam irradiation or X-ray irradiation under a high accelerating voltage condition, and the sensitivity, resolution and resist shape are not satisfied. It has been a challenge to achieve both at the same level.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the performance of a semiconductor device using an electron beam or an X-ray in fine processing, and the sensitivity to the use of the electron beam or the X-ray is considered. It is to provide a positive resist composition for electron beam or X-ray which satisfies the characteristics of the resist and the resolution and the shape of the resist. Furthermore, a high-sensitivity electron beam compatible with the next generation EB irradiator (EB block irradiator or EB stepper (sequential reduction projection irradiator) aimed at improving throughput) with a high acceleration voltage suitable for mass production of semiconductor devices Another object of the present invention is to provide a positive resist composition for X-rays.

[0013]

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 resin having a repeating unit represented by the following general formula (II), and (B) a low molecular weight dissolution inhibiting compound having a molecular weight of 3,000 or less decomposed by the action of an acid. Characteristic positive resist composition for electron beam or X-ray.

[0015]

Embedded image

In the formula, R ₃ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group which may have a substituent. R ₄ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent. A ₁ is a single bond, which may have a substituent, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO
—R ₉ —, —CO—O—R ₁₀ —, —CO—N (R ₁₁ ) —
R ₁₂ - represents a. R ₉ , R ₁₀ and R ₁₂ may be the same or different, and represent a single bond, an ether structure, an ester structure,
A divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have an amide structure, a urethane structure or a ureide structure and may have a substituent. R ₁₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent.

(2) The positive resist composition for electron beam or X-ray according to the above (1), further comprising (C) an alkali-soluble resin. (3) The electron beam or X according to (1) or (2), wherein the resin (A) has a group that is decomposed by the action of an acid to increase the solubility of the resin in an alkali developing solution. Positive resist composition for lines.

(4) The electron beam or X-ray according to any one of (1) to (3), further comprising (D) a compound which generates an acid upon irradiation with an electron beam or X-ray. Positive resist composition.

(5) The resin of (A) comprises at least one repeating unit represented by the general formula (II),
The positive resist composition for electron beam or X-ray according to any one of the above (1) to (4), comprising at least one repeating unit represented by (I) or (IV).

[0020]

Embedded image

In the formula, R ₃ and R ₅ represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or a haloalkyl group which may have a substituent. R ₄ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent. OR ₆ and COOR ₆ represent groups which are decomposed by the action of an acid to increase the alkali solubility of the resin. R ₇ and R ₈ may be the same or different, and include a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group, or an optionally substituted alkyl group, cycloalkyl group, or alkenyl group. , An aralkyl group or an aryl group. A ₁ and A ₂ may be the same or different and may have a single bond, a substituent, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₉ -, -CO
_{-O-R 10 -, - CO} -N (R 11) -R 12 - represents a. R
₉ , R ₁₀ and R ₁₂ may be the same or different and may have a single bond, an ether structure, an ester structure, an amide structure, a urethane structure or a ureide structure, and may have a substituent. Represents a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group.
R ₁₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent. n represents an integer of 1 to 3. A plurality of R ₆ ,
Alternatively, R ₆ and R ₇ or R ₈ may be bonded.

(6) The resin of (A) further has a general formula (V)
Or, the positive resist composition for electron beam or X-ray according to any one of the above (1) to (5), which has at least one repeating unit represented by (VI).

[0023]

Embedded image

In the formula, R ₁₃ represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group or haloalkyl group. R ₁₄ represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or an acyl group, and as OR ₁₄ and COOR ₁₄ , an alkali-soluble group or an acid On the other hand, it represents a group showing substantially no decomposability. R ₁₅ , R ₁₆
May be the same or different, and may be a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group, or an optionally substituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl. Represents a group. A ₃ may have a single bond or a substituent,
Valent alkylene group, alkenylene group, cycloalkylene group or arylene group, or _{-O-CO-R 9, -} , -
_{CO-O-R 10 -,} - it represents a _{CO-N (R 11) -R} 12.
R _{9 to} R ₁₂ have the same meaning as described above. n represents an integer of 1 to 3. Further, a plurality of R _{14 s} or a combination of R ₁₄ and R ₁₅ or R ₁₆ may be combined.

Preferred embodiments are described below. (7) The positive resist composition for electron beam or X-ray, further comprising (E) an acid diffusion inhibitor. (8) The positive resist composition for electron beams or X-rays, wherein the compound of the component (D) is selected from sulfonium or iodonium sulfonate compounds.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. [1] (A) Resin containing a repeating structural unit having a group capable of generating an acid by an electron beam or X-ray represented by the general formula (II) as a component (also referred to as a resin of (A)) The resin of the formula (1) contains a repeating structural unit represented by the general formula (II) and having a group capable of generating an acid by an electron beam or X-ray. The repeating structural unit represented by the general formula (II) generates sulfinic acid or sulfonic acid upon irradiation with an electron beam or X-ray. The resin (A) preferably further contains a repeating structural unit having a group that is decomposed by the action of an acid to increase the alkali solubility of the resin. Further, it preferably contains an alkali-soluble group, an ester group or an ether group which does not substantially show decomposability to an acid.

As the resin (A), specifically, a resin having at least one repeating unit represented by the general formula (II) and at least one repeating unit represented by the general formula (III) or (IV) And more preferably a resin having at least one repeating unit represented by formula (V) or (VI).

In the general formula, R ₃ , R ₅ and R ₁₃ represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group or a haloalkyl group which may have a substituent. R ₄ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group which may have a substituent. OR ₆ , COO
R ₆ represents a group which is decomposed by the action of an acid to increase the alkali solubility of the resin. R ₇ , R ₈ , R ₁₅ , and R ₁₆ may be the same or different, and include a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group, or an optionally substituted alkyl group; Represents a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group.

A ₁ , A ₂ , and A ₃ may be the same or different and may have a single bond, a substituent, a divalent alkylene group, a cycloalkylene group, an arylene group, or —O—. _{CO-R 9 -, - CO} -O-R 10 -, - CO-
And represents N (R ₁₁ ) —R ₁₂ —. R ₉ , R ₁₀ , and R ₁₂ may be the same or different and may have a single bond, an ether structure, an ester structure, an amide structure, a urethane structure, or a ureido structure, and may have a substituent. Good, 2
Represents a valent alkylene group, a cycloalkylene group, or an arylene group. R ₁₁ may have a hydrogen atom or a substituent;
Represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.

Further, R _{3 to} R ₅ , R ₇ , R ₈ , R ₁₁ , R _{13 to} R
_{The 16} alkyl groups are, for example, alkyl groups having 1 to 8 carbon atoms, and specifically, methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, 2-
Preferable examples include an ethylhexyl group and an octyl group. The cycloalkyl group of R ₄ , R ₇ , R ₈ , R ₁₁ , and R _{14 to} R ₁₆ may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferably includes a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an a-pinel group, and a tricyclodecanyl group.

The aryl group of R ₄ , R ₇ , R ₈ , R ₁₁ , and R _{14 to} R ₁₆ is, for example, an aryl group having 6 to 15 carbon atoms, and specifically, a phenyl group, a tolyl group Dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, 9,10-dimethoxyanthryl group and the like. One or more oxo groups may be substituted on the carbon atom forming the aromatic ring of the aryl group (for example, a 1,2-naphthoquino-4-yl group, a 9,10-anthraquino-2-yl group, etc.).
The aralkyl group of R ₄ , R ₇ , R ₈ , R ₁₁ , R _{14 to} R ₁₆ is, for example, an aralkyl group having 7 to 12 carbon atoms, and specifically, a benzyl group, a phenethyl group, a naphthylmethyl And the like.

The alkenyl group of R ₇ , R ₈ and R _{14 to} R ₁₆ is, for example, an alkenyl group having 2 to 8 carbon atoms,
Specifically, a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group can be preferably exemplified. R ₇ ,
The alkoxy group for R ₈ , R ₁₅ , and R ₁₆ is, for example, an alkoxy group having 1 to 8 carbon atoms, specifically, methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy. Groups, a pentoxy group, an allyloxy group and an octoxy group. R
The acyl group of ₇ , R ₈ , R _{14 to} R ₁₆ is, for example, an acyl group having 1 to 10 carbon atoms, and specifically, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, An octanoyl group, a benzoyl group and the like can be preferably mentioned.

The alkylene group of A _{1 to} A ₃ , R ₉ , R ₁₀ and R ₁₂ is preferably a methylene group, an ethylene group, a propylene group, a butylene group which may have a substituent,
Examples thereof include those having 1 to 8 carbon atoms such as a hexylene group and an octylene group. As the alkenylene group for A _{1 to} A ₃ , R ₉ , R ₁₀ and R ₁₂ , those having 2 to 6 carbon atoms such as an ethenylene group, a propenylene group and a butenylene group which may have a substituent are preferred. No. A _{1 to} A ₃ , R ₉ ,
As the cycloalkylene group for R ₁₀ and R ₁₂ , those having 5 to 8 carbon atoms, such as a cyclopentylene group and a cyclohexylene group, which may have a substituent, are preferred.
As the arylene group for A _{1 to} A ₃ , R ₉ , R ₁₀ and R ₁₂ ,
Preferable examples include those having 6 to 15 carbon atoms such as a phenylene group, a tolylene group and a naphthylene group which may have a substituent.

The ring formed by combining a plurality of R ₆ , R ₆ and R ₇ or R ₈ , and a plurality of R ₁₄ , or R ₁₄ and R ₁₅ or R ₁₆ is a benzofuran ring, a benzofuran ring or a benzofuran ring. Examples thereof include a 4- to 7-membered ring containing an oxygen atom constituting a structure such as a dioxonol ring and a benzopyran ring.

OR₆, COOR₆By the action of the acid represented by
As a group that decomposes and shows alkali solubility, specifically,
-OC (R₀₁) (R₀₂) (R₀₃), -OC (R₀₁)
(R ₀₂) (OR₀₄), -O-COO-C (R₀₁)
(R₀₂) (R₀₃), -OC (R₀₅) (R₀₆) COO-
C (R₀₁) (R₀₂) (R₀₃), -COO-C (R₀₁)
(R₀₂) (R₀₃), -COO-C (R₀₁) (R₀₂) (O
R₀₄) And R₀₁~ R₀₃, R ₀₅, R₀₆Is a hydrogen atom,
Alkyl group which may have a substituent, cycloalkyl
Group, alkenyl group, aralkyl group, or aryl group
And R₀₄Is an alkyl group which may have a substituent,
Cycloalkyl, alkenyl, aralkyl,
Represents an aryl group. Preferred alkyl group, cycloa
Alkyl, alkenyl, aralkyl, or ant
Examples of the hydroxyl group include those described above. Also R₀₁~ R
₀₄Are bonded to form a cyclopentane ring,
Xan ring, tetrahydrofuran ring, tetrahydropyran
A 4- to 7-membered ring such as a ring may be formed.

The substituents substituted on these groups include:
Those having active hydrogen such as an alkyl group, a cycloalkyl group, an aryl group, 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, an iodine atom ), Alkoxy groups (methoxy, ethoxy, propoxy, butoxy groups, etc.), thioether groups, acyl groups (acetyl groups, propanoyl groups, benzoyl groups, etc.), acyloxy groups (acetoxy groups, propanoyloxy groups, benzoyloxy groups) And the like, an alkoxycarbonyl group (such as a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group), a cyano group, a nitro group, and an α-campanyl group. Here, the alkyl group, cycloalkyl group, and aryl group include those described above, but the alkyl group may be further substituted with a fluorine atom, or may have an amide structure. When two or more of the above further substituents are substituted, two of them may combine to form a ring. The ring may contain an oxo group.

The content of the repeating structural unit represented by the general formula (II) is 0.1 to 80 mol%, preferably 1 to 50 mol%, more preferably 3 to 2 mol% in the whole polymer composition.
It is used in the range of 0 mol%. Formula (III) or (I
The content of the repeating structural unit represented by V) is from 5 to 80 mol%, preferably from 10 to 50 mol% in the whole polymer composition.
Mol%, more preferably in the range of 20 to 40 mol%. The content of the repeating structural unit represented by the general formula (V) or (VI) is 0 to 80 mol%, preferably 10 to 70 mol%, more preferably 3 to 3 mol% in the whole polymer composition.
It is used in the range of 0 to 60 mol%.

The resin of the present invention (A) may be copolymerized with other polymerizable monomers for the purpose of further improving the performance of the positive resist of the present invention, in addition to the above-mentioned repeating structural units. .

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-alkylmethacrylamide (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, for example, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, 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.

Specific examples of the repeating structural units represented by formulas (II) to (VI) are shown below, but the present invention is not limited thereto.

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

Each of the repeating structural units represented by the above specific examples may be used alone or in combination.

The preferred molecular weight of the resin (A) of the present invention having the above-mentioned repeating structural unit is from 1,000 to 1,000 on a weight average.
500,000, more preferably 3,000 to 5
Used in the range of 0000. Molecular weight distribution is 1-10
, Preferably 1 to 3, more preferably 1 to 1.5
Are used. The smaller the molecular weight distribution, the smoother the resolution, the resist shape, and the side wall of the resist pattern, and the better the roughness.

The amount of the resin (A) of the present invention is from 5 to 95% by weight, preferably from 10 to 95% by weight, based on the total solids of the composition.
To 85% by weight, more preferably 20 to 75% by weight.

[2] Compound of the present invention (D) which generates an acid upon irradiation with an electron beam or X-ray In the present invention, the resin (A) may also serve as a compound which generates an acid. The compound which generates an acid by irradiation with an electron beam or X-ray of the present invention (D) shown in (1) can be used. Electron beam or X that can be used in the present invention
Compounds that decompose upon irradiation with a ray to generate an acid include:
Known light (400 to 200 n) used for a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a micro resist.
m ultraviolet rays, far ultraviolet rays, particularly preferably g-rays, h-rays,
Compounds that generate an acid by i-ray, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray, molecular beam or ion beam, and a mixture thereof can be appropriately selected and used.

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, JP-A-3-140109, etc., compounds which generate sulfonic acid by photodecomposition represented by iminosulfonate, etc.
Disulfone compounds described in JP-A-61-166544 and the like can be mentioned.

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, 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 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).

[0073]

Embedded image

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
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.

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

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

[0079]

Embedded image

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 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.

Z ⁻ represents an anion, specifically, an alkyl sulfonic acid, a cycloalkyl sulfonic acid, a perfluoroalkyl sulfonic acid, an aryl sulfonic acid which may have a substituent (for example, 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.

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

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

[0097]

Embedded image

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. 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.

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

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

[0106]

Embedded image

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.

[0108]

Embedded image

The amount of the compound capable of generating an acid upon irradiation with an electron beam or X-ray of the present invention (D) is usually 0.1 to 20% by weight based on the total solid content of the composition of the present invention. And preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight. These compounds may be used alone or in combination of two or more.

[3] Low-molecular-weight dissolution inhibiting compound having a molecular weight of 3000 or less which is decomposed by the action of an acid of the present invention (B) In the present invention, the compound (B) has a group decomposable by an acid, It is a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, whose dissolution rate in a developer is increased by the action of an acid.

The preferred compound (B) to be incorporated in the composition of the present invention has at least two acid-decomposable groups in its structure, and the position at which the distance between the acid-decomposable groups is the longest. Is a compound having at least 8 bonding atoms excluding an acid-decomposable group. More preferred present invention (B)
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, has at least 10 bonding atoms excluding the acid-decomposable group.
, Preferably at least 11, more preferably at least 12 compounds, or at least three acid-decomposable groups, and at the position where the distance between the acid-decomposable groups is the longest, the acid-decomposable group is Excluding at least 9 connecting atoms
, Preferably at least 10 and more preferably at least 11 via. 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 compound of the present invention (B) has three or more, preferably four or more acid-decomposable groups, the compound having two acid-decomposable groups also has When the functional groups 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, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in the compound (3), 12 bonding atoms.

[0112]

Embedded image

The acid-decomposable dissolution-inhibiting compound of the present invention (B) may have a plurality of acid-decomposable groups on one benzene ring, but preferably one benzene ring. It is a compound composed of a skeleton having one acid-decomposable group on the ring. Further, the molecular weight of the acid-decomposable dissolution inhibiting compound of the present invention is 3,000 or less, preferably 30
It is 0 to 3,000, more preferably 500 to 2,500.

[0114] In a preferred embodiment of the present invention, groups capable of decomposing by an acid, i.e. -COO-A ^0, examples of the group include a -O-B ⁰ group, -R ⁰ -COO-A ^0, or -Ar −
A group represented by O-B ⁰ and the like. Where A ⁰ is −C
( ^R01 ) ( ^R02 ) ( ^R03 ), -Si ( ^R01 ) ( ^R02 )
Shows the (R ^{0 3)} or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰ represents A ⁰ or a —CO—OA ⁰ group.
R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group;
⁰⁶ represents an alkyl group or an aryl group. Where R ⁰¹
At least two of to R ⁰³ is a group other than a hydrogen atom,
Further, two groups out of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ may combine to form a ring. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

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.

The compounds of the present invention (B) are preferably those described in JP-A-1-289946 and JP-A-1-289994.
7, JP-A-2-2560, JP-A-3-128959
JP-A-3-158855, JP-A-3-17935
No. 3, JP-A-3-191351, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
No. 253, JP-A-3-200254, JP-A-3-20
0255, JP-A-3-259149, JP-A-3-2
No. 79958, JP-A-3-279959, JP-A-4-
1650, JP-A-4-1651, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
No. 7, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-23079
No. 0, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-2515
7, Japanese Patent Application No. 4-52732, 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
A part of or all of the phenolic OH groups of the polyhydroxy compound described in the specification such as No. 5 above;
-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.

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

Here, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ and R ¹³⁰ may be the same or different, and represent a hydrogen atom, —R ⁰ —COO
—C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or —CO—O—C (R
⁰¹ ) ( ^R02 ) ( ^R03 ), provided that ^R0 , ^R01 , ^R02 and R
The definition of ⁰³ is the same as above.

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

[0126]

Embedded image

[0127] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ¹⁵³ or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,, R ^99, R ¹⁰³ ~ R ¹⁰⁷ , R ¹⁰⁹ , R ^{111 to} R ¹¹⁸ , R ^{121 to} R
¹²³ , R ^{128 to} R ¹²⁹ , R ^{131 to} R ¹³⁴ , R ^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different, and represent a hydrogen atom, a hydroxyl group,
Alkyl group, alkoxy group, acyl group, acyloxy group,
Aryl group, aryloxy group, aralkyl group, aralkyloxy group, halogen atom, nitro group, carboxyl group, cyano group, or —N (R ¹⁵⁵ ) (R ¹⁵⁶ ) (where R ¹⁵⁵ and R ^{156 are} H, alkyl R ¹¹⁰ : single bond, alkylene group, or

[0128]

Embedded image

R ¹⁵⁷ and R ¹⁵⁹ may be the same or different;
Single bond, 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 a carboxyl group, provided that the hydroxyl group is an acid-decomposable group (for example, a t-butoxycarbonylmethyl group, a tetrahydropyranyl group, a 1-ethoxy-1-ethyl group,
(1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ¹²⁰ : may be the same or different,
A methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group is 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. R ^{135 to} R ¹³⁷ may be the same or different and may be 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 ) (R ⁰² )
(R ⁰³ ) or -CO-OC (R ⁰¹ ) (R ⁰² )
(R ⁰³ ), or

[0131]

Embedded image

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

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image

In the present invention, the component (B) includes, among the above, general formulas [II], [III], [VIII] and [X]
[I], [XII], [XIII], [XVI] and [XV] are preferable, and more preferably a compound represented by the general formula [II]
I], [VIII], [XII], [XIII], [XVI], [XV]
It has the structure shown by. Specific examples of preferred compound skeletons are shown below.

[0138]

Embedded image

[0139]

[Of 60]

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

[0149]

Embedded image

[0150]

Embedded image

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

[0152]

Embedded image

Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
May not be the same group. In the present invention, the content of the component (B) in the composition is usually 5 to 50% by weight, preferably 10 to 50% by weight, based on the total solid content of the composition.
-40% by weight, more preferably 15-30% by weight
It is.

(C) Alkali-soluble resin In the present invention, it is preferable to use (C) an alkali-soluble resin for the composition. Examples of the alkali-soluble resin (C) used in the present invention include 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, partially O-alkylated product relative to hydroxyl group of polyhydroxystyrene (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, etc.) or O-acylated product (for example, 5 to 30 mol%)
O-acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacryl Examples thereof include, but are not limited to, system resins and derivatives thereof, and polyvinyl alcohol derivatives. Particularly preferred (C) alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-
Polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially O-alkylated or O-acylated polyhydroxystyrene, styrene-hydroxystyrene copolymer, α-methyl It is a styrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

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

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

The 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. In the present invention, these alkali-soluble resins (C) may be used in combination of two or more. In the present invention, the content of the alkali-soluble resin (C) in the composition is usually from 0 to 90 with respect to the total solid content of the composition.
Weight, preferably 15-80 weight, more preferably 30-70 weight.

[4] Acid Diffusion Inhibitor of the Present Invention (E) The composition of the present invention has a performance variation (e.g., formation of a T-top shape of a pattern, sensitivity) over time from irradiation of electron beam or X-ray to heat treatment. Acid diffusion for the purpose of preventing fluctuations in performance over time after application, fluctuations in pattern line width, etc.), and overdiffusion of acid (deterioration of resolution) during heat treatment after irradiation with electron beams or X-rays. Preferably, an inhibitor is added. The acid diffusion inhibitor is an organic basic compound, for example, an organic basic compound containing basic nitrogen, and has a pK of conjugate acid.
Compounds having an a value of 4 or more are preferably used. Specifically, there can be mentioned the structures of the following formulas (A) to (E).

[0159]

Embedded image

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, and 1 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.

[5] Other components used in the composition of the present invention (1) Sensitizer The composition of the present invention improves the generation efficiency or the amount of acid generated upon irradiation with an electron beam or X-ray. A sensitizer may be used for the purpose. As such a sensitizer, a compound capable of generating secondary electrons by absorbing the energy of an electron beam or an X-ray is preferable. Specifically, it is an aromatic compound having a high electron density, and examples thereof include a monocyclic or polycyclic compound such as benzene, naphthalene, anthracene, and pyrene substituted with an electron donating group such as an alkoxy group or a hydroxy group.

(2) Solvents The composition of the present invention is dissolved in a solvent capable of dissolving each of the above 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-dimethylformamide, dimethylsulfoxide, N-methyl Pyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

(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 surfactant such as Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), and organosiloxane polymer KP3
No. 41 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymerized polyflow No. 41 75, N
o. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

The amount of these surfactants is usually 2% by weight per 100% by weight of the solid content in the composition of the present invention.
Or less, preferably 1% by weight or less. These surfactants may be added alone or in some combination.

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 developing solution for the positive photoresist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, and the like.
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.

[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 Monomer of Structural Example (II-2) Having Disulfone Group)] 21.6 g (0.110 mol) of sodium p-toluenesulfinate monohydrate was mixed with 80 ml of ion-exchanged water. And stirred at room temperature for 4 hours.
-20.3 g of styrenesulfonyl chloride (0.100
Mol) was added dropwise. Stirring was continued at room temperature for another 5 hours. After filtering the precipitated white solid, washing with water and drying,
Purification was performed by column chromatography (filler: silica gel, developing solution: hexane / ethyl acetate). White powder 1
5.7 g was obtained, and it was confirmed by NMR measurement that the structure was 4-styryl tolyl disulfone.

[Synthesis Example 2 (Resin (A-1) of the present invention,
(Synthesis of (A-2))] 4.76 g of 4-butoxystyrene
(0.027 mol) and 0.97 g (0.003 mol) of 4-styryl tolyl disulfone were dissolved in 30 ml of 1-methoxy-2-propanol.
At 0 ° C., 50 mg of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (trade name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.), 11.1 g of 4-butoxystyrene
(0.063 mol) and a solution of 2.26 g (0.007 mol) of 4-styritolyldisulfone in 70 ml of 1-methoxy-2-propanol were added dropwise over 2 hours. 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. After allowing the reaction solution to cool, it was poured into 2 L of ion-exchanged water with vigorous stirring to precipitate a white resin (A-1) of the present invention. When the composition of the resin (A-1) was examined by C ¹³ -NMR measurement, the structural example (II-2) / (III
-1) = 10/90. Obtained resin (A-1)
After drying 18.5 g under reduced pressure, a part of 4-butoxy group was deprotected with a catalytic amount of hydrochloric acid in toluene to obtain 14.3 g of the resin (A-2) of the present invention. The C ¹³ -NMR measurement, was examined the composition of the resin (A-2), the structure example in a molar ratio (II-2) / (III -1) / (V-1) = 10/2
It was confirmed to be 6/64. According to GPC measurement, the molecular weights of (A-1) and (A-2) were determined by weight average (M
w: polystyrene standard) 12,100, 1
1,500.

[Synthesis Example 3 (Synthesis of Resin (A-3) of the Present Invention)] The resin of 4-butoxystyrene / 4-styryl tolyldisulfone obtained in the same manner as in Synthesis Example 1 was dissolved in toluene.
The 4-butoxy group was deprotected using a catalytic amount of hydrochloric acid. 12.6 g of the obtained resin was dissolved in 80 ml of THF, and 2.12 g (0.03 g) of ethyl vinyl ether was added thereto.
0 mol), and a catalytic amount of p-toluenesulfonic acid was further added, followed by reaction at 40 ° C. for 8 hours. After neutralization with pyridine, the mixture was poured into 2 L of ion-exchanged water with vigorous stirring to precipitate a white resin. The precipitated resin was separated by filtration and dried under reduced pressure to obtain 14.1 g of the resin (A-3) of the present invention. The C ¹³ -NMR measurement, was examined the composition of the resin (A-3), structural example (II-2) in a molar ratio / (III-2) / ( V-1) = 9/31
/ 60. Also, by GPC measurement,
It was confirmed that the molecular weight of (A-3) was 12,100 by weight average (Mw: polystyrene standard).

[Synthesis Examples 4 to 20 (Synthesis of Resin (A) of the Present Invention)] The resins of the present invention (A) shown in Table 1 were synthesized in the same manner.

[0177]

[Table 1]

Examples 1 to 11 and Comparative Examples 1 to 3 (1) Application of resist The components shown in Table 2 below were dissolved in 8.5 g of propylene glycol monomethyl ether acetate, and triphenylimidazole was added thereto. 0.01 g and 0.01 g of Megafac R08 (manufactured by Dainippon Ink Co., Ltd.) as a surfactant were added to prepare a resist composition of the present invention. Each sample solution was filtered through a 0.1 μm Teflon (registered trademark) filter, and then applied on a hexamethyldisilazane-treated silicon wafer by a spin coater to form a sample.
The film was heated and dried on a vacuum contact hot plate at 90 ° C. for 90 seconds to obtain a resist film having a thickness of 0.3 μm.

[0179]

[Table 2]

In Table 2, R of the dissolution inhibitor is -C
H ₂ COOC ₄ H ₉ (t). The resin used in the comparative example has the following composition in a molar ratio.

Resin (1): Structural example (III-2) / (V-1) = 35/65, molecular weight Mw = 11,500 Resin (2): Structural example (III-6) / (V-1) Resin (3): structural example (V-2), molecular weight Mw = 10,700 resin (4): structural example (V-1) / styrene = 85/15, molecular weight Mw = 12,400

(2) Preparation 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 3 shows the results of the performance evaluation.

[0183]

[Table 3]

From the results shown in Table 3, the positive resist composition using the resin (A) of the present invention having a disulfone group has higher sensitivity and better resolution and profile than the comparative example having no such group. You can see that.

[Examples 12 to 14 and Comparative Example 4] A resist film formed in the same manner as described above using the compositions of Examples 2, 5, and 7 and Comparative Example 1 was applied with an acceleration voltage of 100 KeV. Irradiation was performed using an electron beam drawing apparatus under the conditions. 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 4 shows the results of the evaluation performed in the same manner as in the above example.

[0186]

[Table 4]

From the results shown in Table 4, it can be seen that the positive resist composition of the present invention exhibits better sensitivity and resolution than the composition of the comparative example even when irradiated with an electron beam at a high accelerating voltage.

[0188]

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

Continued on the front page F-term (reference) 2H025 AA01 AA02 AA03 AB16 AC05 AC06 AD03 BE00 BE10 BG00 CB14 CB15 CB16 CB17 CB41 CC20 4J002 BC02X BC11X BC12W BC12X BE02X BG07W BG07X BG13W CC04X EV2 EVEV027 EB0 ELEVON ELEVEL ELEVEL FD206

Claims (6)

[Claims] 1. It comprises (A) a resin having a repeating unit represented by the following general formula (II), and (B) a low-molecular-weight dissolution inhibiting compound having a molecular weight of 3,000 or less decomposed by the action of an acid. Or a positive resist composition for X-rays. Embedded image In the formula, R ₃ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group which may have a substituent. R ₄ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent. A ₁ may have a single bond or a substituent,
Valent alkylene group, alkenylene group, cycloalkylene group or arylene group, or _{-O-CO-R 9, -} , -
_{CO-O-R 10 -,} - CO-N (R 11) -R 12 - represents a. R ₉ , R ₁₀ and R ₁₂ may be the same or different,
A single bond, or an ether structure, an ester structure, an amide structure, a urethane structure or a ureido structure, which may have a substituent, a divalent alkylene group,
Represents an alkenylene group, a cycloalkylene group or an arylene group. R ₁₁ may have a hydrogen atom or a substituent;
Represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. 2. The positive resist composition for electron beam or X-ray according to claim 1, further comprising (C) an alkali-soluble resin. 3. The resin of (A) is decomposed by the action of an acid,
3. The positive resist composition for electron beam or X-ray according to claim 1, further comprising a group that increases the solubility of the resin in an alkali developing solution. 4. The positive resist for electron beam or X-ray according to claim 1, further comprising (D) a compound which generates an acid upon irradiation with an electron beam or X-ray. Composition. 5. The resin of (A) having at least one repeating unit represented by the general formula (II) and at least one repeating unit represented by the general formula (III) or (IV). The positive resist composition for electron beams or X-rays according to claim 1. Embedded image In the formula, R ₃ and R ₅ represent a hydrogen atom, a halogen atom, a cyano group,
Represents an alkyl group or a haloalkyl group which may have a substituent. R ₄ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent. OR ₆ and COOR ₆ represent groups which are decomposed by the action of an acid to increase the alkali solubility of the resin. R ₇ and R ₈ may be the same or different, and include a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group, or an optionally substituted alkyl group, cycloalkyl group, or alkenyl group. , An aralkyl group or an aryl group. A ₁ and A ₂ may be the same or different and may have a single bond, a substituent, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₉ -, -CO-OR ₁₀ -,-
Represents CO—N (R ₁₁ ) —R ₁₂ —. R ₉ , R ₁₀ , and R ₁₂ may be the same or different and may have a single bond, an ether structure, an ester structure, an amide structure, a urethane structure, or a ureido structure, and may have a substituent. Good represents a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group. R ₁₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent. n represents an integer of 1 to 3. A plurality of R _{6 s} , or R ₆ and R ₇ or R ₈
May be combined. 6. The electron beam according to claim 1, wherein the resin (A) further has at least one repeating unit represented by the general formula (V) or (VI). Or a positive resist composition for X-rays. Embedded image In the formula, R ₁₃ represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group or haloalkyl group. R ₁₄ represents a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or an acyl group, OR _14, C
OOR _{14 represents} an alkali-soluble group or a group which does not substantially decompose in an acid. R ₁₅ and R ₁₆ may be the same or different, and include a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group, or an optionally substituted alkyl group, a cycloalkyl group, or an alkenyl group. , An aralkyl group or an aryl group. A
₃ is a single bond, which may have a substituent, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₉ — and —CO—O—R ₁₀
-, - it represents a _{CO-N (R 11) -R} 12. R _{9 to} R ₁₂ have the same meaning as described above. n represents an integer of 1 to 3. Further, a plurality of R _{14 s} or a combination of R ₁₄ and R ₁₅ or R ₁₆ may be combined.