JP2001281864A - Resist composition for electron beam or x-ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide positive type and negative type resist compositions for electron beams or X-rays having high resolving power without causing the lowering of sensitivity and capable of giving a pattern profile excellent in rectangularity and to provide positive type and negative type resist compositions for electron beams or X-rays excellent in appliability (intrasurface uniformity). SOLUTION: The objective resist composition for electron beams or X-rays contains (a) a compound which generates an acid when irradiated with electron beams or X-rays and (b) electrically conductive fine particles or at least one selected from the group comprising electrically conductive organic polymers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist composition, and more particularly, to a resist composition for an electron beam or an X-ray which has an excellent pattern profile obtained by exposure to an electron beam or an X-ray and has an excellent resolution.

[0002]

2. Description of the Related Art The degree of integration of integrated circuits is increasing, and in the manufacture of semiconductor substrates such as VLSIs, the processing of ultrafine patterns having a line width of less than half a minute is required. It has become. In order to satisfy the necessity, the wavelength used in 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. Furthermore, 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 technique, and it is desired to develop positive and negative resist compositions capable of achieving a high sensitivity, a high resolution and a rectangular profile. ing.

[0004]

However, when an ultrafine pattern is processed by an electron beam or X-ray, there is a problem that the resist composition is charged and the pattern is disturbed. Accordingly, an object of the present invention is to provide positive and negative resist compositions for electron beams or X-rays having a high resolution and capable of giving an excellent rectangular pattern profile without causing a decrease in sensitivity. Is to do. Another object of the present invention is to provide positive and negative resist compositions for electron beams or X-rays having excellent coatability (in-plane uniformity).

[0005]

That is, the above-mentioned object of the present invention is attained by preparing a positive and negative resist composition for electron beam or X-ray, which will be described in detail below, using a specific antistatic agent. Is achieved. (1.) It is characterized by containing (a) a compound generating an acid upon irradiation with an electron beam or X-ray, and (b) at least one selected from the group consisting of conductive fine particles or conductive organic polymers. Electron or X-ray resist composition.

(2.) The (b) conductive fine particles or conductive organic polymer is at least one selected from the group consisting of the following substances (1) to (8): 1. The electron beam or X-ray resist composition according to 1). (1) carbon black or carbon fibers (2) optionally substituted carbon nanotubes (3) polyparaphenylene derivative (4) polythiophene derivative (5) polyparaphenylene vinylene derivative (6) poly N-vinylcarbazole derivative (7 ) Poly (meth) acrylate derivatives having a quaternary ammonium salt structure in the side chain (8) Polystyrene derivatives having a quaternary ammonium salt structure in the side chain

(3.) The compound (a) which generates an acid upon irradiation with an electron beam or X-ray, represented by the following general formulas (I) to (II)
(1) wherein the compound is at least one compound selected from the group consisting of compounds represented by (I).
Or the positive and negative resist compositions for electron beam or X-ray according to (2.).

Embedded image (Wherein, R _{1 to} R ₃₇ are the same or different and are each a hydrogen atom, an alkyl group which may be branched or cyclic, an alkoxy group which may be branched or cyclic, a hydroxy group, a halogen atom Or —S—R ₃₈ group.
₃₈ is an alkyl group which may be branched or cyclic,
Represents an aryl group. Further, at least two or more members out of R _{1 to} R ₃₇ may combine to form a ring containing one or more members selected from a single bond, carbon, oxygen, sulfur and nitrogen. X ^- represents at least one optionally substituted methanesulfonic acid, butanoic acid, octanoic acid, benzenesulfonic acid, an anion of naphthalenesulfonic acid or anthracenesulfonic acid. )

(4.) In the above general formulas (I) to (III), X ^- is a linear, branched or cyclic alkyl group substituted by at least one fluorine atom and at least one fluorine atom. A linear, branched or cyclic alkoxy group substituted with one fluorine atom, an acyl group substituted with at least one fluorine atom, an acyloxy group substituted with at least one fluorine atom, Substituted sulfonyl group Sulfonyloxy group substituted with at least one fluorine atom Sulfonylamino group substituted with at least one fluorine atom Aryl group substituted with at least one fluorine atom At least one fluorine atom A substituted aralkyl group and an alkoxycarbonyl group substituted with at least one fluorine atom Above, wherein the al selected benzenesulfonic acid having at least one, the anion of naphthalenesulfonic acid or anthracenesulfonic acid, (1)
The resist composition for electron beam or X-ray according to any one of (1) to (3.).

(5) (d) a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group which can be decomposed by the action of an acid and whose solubility in an alkali developing solution is increased by the action of an acid; The resist composition for an electron beam or X-ray according to any one of the above (1) to (4.), wherein the composition is a mold.

(6.) From the group consisting of (c-1) a resin having an aromatic ring and a group capable of decomposing under the action of an acid in the repeating unit, and having increased solubility in an alkali developing solution under the action of an acid. The resist composition for an electron beam or X-ray according to any one of the above (1) to (5), comprising at least one selected from the group consisting of a positive type.

(7.) (c-2) at least one selected from the group consisting of an alkali-soluble resin having an aromatic ring in a repeating unit,
(1.) wherein the composition is a positive type.
The resist composition for an electron beam or X-ray according to any one of (1) to (5.).

(8.) (f) It is a positive type, containing at least one compound selected from a vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound and an aldehyde compound. The resist composition for electron beam or X-ray according to any one of (1.) to (7.).

(9.) The resist composition for electron beam or X-ray according to (8), wherein the compound (f) is a compound represented by the general formula (A).

Embedded image R _a , R _b , R _c ; which may be the same or different, a hydrogen atom,
It represents an alkyl group or an aryl group which may have a substituent, and two of them may combine to form a saturated or olefinically unsaturated ring. R _d represents an alkyl group or a substituted alkyl group.

(10.) (g) The electron beam or the electron beam according to any one of (1) to (4), wherein the electron beam or negative electrode contains a crosslinking agent which reacts under the action of an acid and is of a negative type. X-ray resist composition.

(11.) (c-2) wherein the repeating unit contains an alkali-soluble resin having an aromatic ring in the repeating unit.
3. The resist composition for electron beam or X-ray according to claim 1.

(12.) The alkali-soluble resin having an aromatic ring in the repeating unit (c-2) is selected from the group consisting of resins represented by the following general formulas (ca) to (ce): The resist composition for electron beam or X-ray according to (11), which is at least one selected from the group consisting of:

Embedded image In general formulas (ca) to (cd), R ₂₀₁ to
R ₂₀₅ , R _{301 to} R ₃₀₅ , R _{401 to} R ₄₀₅ , R _{401 to} R
₄₀₅ each independently represents a hydrogen atom or a methyl group. R ₂₀₆
To R ₂₁₁ , R _{306 to} R ₃₁₁ , R _{406 to} R ₄₁₁ , R _{506 to} R ₅₁₁
Each independently represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms, or -OR ₂₁₃ (R ₂₁₃ represents a hydrogen atom or a group which is decomposed by the action of an acid (also referred to as an acid-decomposable group) .). R ₂₁₂ , R ₃₁₂ , R ₄₁₂ , R
₅₁₂ represents —COOR ₂₁₄ (R ₂₁₄ represents a hydrogen atom or an acid-decomposable group). 0 <l ≦ 100 0 ≦ m, n, o, p <100 l + m + n + o + p = 100 In the general formula (ce), R ₆₀₁ represents a hydrogen atom or a methyl group. L represents a divalent linking group. R _f , R _g , R
_h , R _i , R _y , and R _z each independently represent a carbon number of 1 to 1;
2 represents a linear, branched, or cyclic alkyl group, alkenyl group, aryl group, aralkyl group, or hydrogen atom. These are connected to each other to form a carbon atom having 24 carbon atoms.
The following 5- or more-membered ring may be formed. r, s, t, u, v, w, x
Represents an integer from 0 to 3, and satisfies r + w + x = 0, 1, 2, 3.

(13.) (h) An electron beam or X-ray according to any one of (1) to (12) above, which contains a fluorine-based and / or silicon-based surfactant. Resist composition.

(14.) (i) It contains at least one of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate and propylene glycol monomethyl ether as a solvent. The resist composition for electron beam or X-ray according to any one of the above.

First, the components of the electron beam or X-ray positive resist composition will be described. [I] (a) Compound that generates an acid by irradiation with an electron beam or X-ray (hereinafter, also referred to as “component (a)”) As the component (a), a compound that generates an acid by irradiation with radiation Any of them can be used, but the compounds represented by formulas (I) to (III) are preferable. [I-1] in the general formula (I) ~ (III) compound represented by the general formula (I) ~ (III), R 1 ~R 38 linear,
As the branched alkyl group, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-
Examples thereof include those having 1 to 4 carbon atoms such as -butyl group and t-butyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms which may have a substituent, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. Examples of the linear or branched alkoxy group represented by R _{1 to} R ₃₇ include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. Such a C1-C4 thing is mentioned. Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. Examples of the halogen atom for R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group for R ₃₈ include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. Preferred as these substituents are alkoxy groups having 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, iodine atom), aryl groups having 6 to 10 carbon atoms, and alkenyl groups having 2 to 6 carbon atoms. , A cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, a nitro group and the like.

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

In the general formulas (I) to (III), X ⁻ is preferably an anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from the following groups. At least one fluorine atom, a linear, branched or cyclic alkyl group substituted with at least one fluorine atom; a linear, branched or cyclic alkoxy group substituted with at least one fluorine atom. Acyl group substituted with a fluorine atom acyloxy group substituted with at least one fluorine atom sulfonyl group substituted with at least one fluorine atom sulfonyloxy group substituted with at least one fluorine atom at least one fluorine Sulfonylamino group substituted with an atom Aryl group substituted with at least one fluorine atom Aralkyl group substituted with at least one fluorine atom and alkoxycarbonyl group substituted with at least one fluorine atom

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

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

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

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

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

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

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

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

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

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

[0032] The most preferred X ^- is a fluorine-substituted benzenesulfonic acid anion, among others pentafluorobenzenesulfonic acid anion is particularly preferred.

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

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

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

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

[0040]

Embedded image

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

[0042]

Embedded image

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

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

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

(Synthesis of Triphenylsulfonium pentafluorobenzenesulfonate: Synthesis of Specific Example (I-1)) Diphenylsulfoxide 509 was converted to benzene 800 m
1 and 200 g of aluminum chloride was added thereto and refluxed for 24 hours. The reaction solution was slowly poured into 2 L of water, and 400 ml of concentrated hydrochloric acid was added thereto, followed by heating at 70 ° C. for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate,
After filtration, 200 g of ammonium iodide was added to 400 m of water.
The solution dissolved in 1 was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodide. 30.5 g of triphenylsulfonium iodide was added to 1000 ml of methanol.
And 19.1 g of silver oxide was added to the solution, followed by stirring at room temperature for 4 hours. The solution was filtered, and an excess amount of the solution of tetramethylammonium pentafluorobenzenesulfonate synthesized above was added thereto. The reaction solution was concentrated, and this was dissolved in 500 ml of dichloromethane.
% Tetramethylammonium hydroxide aqueous solution and water. After drying the organic phase over anhydrous sodium sulfate,
Concentration provided triphenylsulfonium pentafluorobenzenesulfonate.

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

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

[I-2] Other photoacid generators that can be used as component (a) In the present invention, the component (a) is decomposed by irradiation with radiation to generate an acid as described below. Compounds can also be used. In the present invention, the component (a)
In addition, the compounds represented by the following general formulas (I) to (III) may be used in combination with the following compounds which decompose upon irradiation with radiation to generate an acid. The amount of the photoacid generator that can be used in combination with the compounds represented by the above general formulas (I) to (III) in the present invention is usually in a molar ratio (component (a) / other acid generator). 100 / 0-20
/ 80, preferably 100/0 to 40/60, and more preferably 100/0 to 50/50. The total content of the component (a) is usually from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, based on the solid content of the positive electrode or X-ray resist composition of the present invention. More preferably, it is 1 to 7% by weight.

Such photoacid generators are used in photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, microresists, and the like. Known compounds that generate an acid upon irradiation with radiation and mixtures thereof can be appropriately selected and used.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
Salt, DCNecker etal, Macrom
olecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent No.
Nos. 4,069,055 and 4,069,056, and phosphonium salts described in JVCrivello et al., Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
No. 4,143, U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17, 73 (1985),
JVCrivelloetal.J.Org.Chem., 43, 3055 (1978), WRWa
tt etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (19
84), JVCrivello etal, Polymer Bull., 14,279 (198
5), JVCrivello etal, Macromorecules, 14 (5), 1141 (19
81), JVCrivello etal, J. PolymerSci., Polymer Che
m.Ed., 17,2877 (1979), European Patent Nos. 370,693, 3,90
No. 2,114, No. 233,567, No. 297,443, No. 297,442, U.S. Pat.Nos. 4,933,377, 161,811, No. 410,201, No. 3
No. 39,049, No. 4,760,013, No. 4,734,444, No. 2,833,82
No. 7, Dokoku Patent Nos. 2,904,626, 3,604,580, 3,60
No. 4,581, etc., sulfonium salt, JVCrivello eta
l, Macromorecules, 10 (6), 1307 (1977), JVCrivello et
al, J. PolymerSci., Polymer Chem. Ed., 17,1047 (1979)
Selenonium salts, CSwen et al, Teh, Proc.Co
Onium salts such as arsonium salts described in nf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.
No., JP-B-46-4605, JP-A-48-36281, JP-A-55-3
No. 2070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401
No., JP-A-63-70243, organic halogen compounds described in JP-A-63-298339, K. Meier et al., J. Rad.Curing, 13
(4), 26 (1986), TPGill et al., Inorg.Chem., 19, 3007 (1
980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896), and organometallic / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polymer Sci. ., 25,753 (1987), ER
eichmanis etal, J.Pholymer Sci., Polymer Chem.Ed., 2
3,1 (1985), QQ Zhu et al., J. Photochem., 36, 85, 39, 317 (1
987), B. Amit etal, Tetrahedron Lett., (24) 2205 (197
3), DHR Barton et al., J. Chem Soc., 3571 (1965), PM
Collins etal, J. Chem.SoC., Perkin I, 1695 (1975), M. Ru
dinstein etal, Tetrahedron Lett., (17), 1445 (1975),
JWWalker etal J. Am. Chem. Soc., 110, 7170 (1988), SC
Busman et al., J. Imaging Technol., 11 (4), 191 (1985), H.
M. Houlihan et al, Macormolecules, 21, 2001 (1988), PMC
ollins et al., J. Chem. Soc., Chem. Commun., 532 (1972), SH
ayaseetal, Macromolecules, 18, 1799 (1985), E. Reichmani
s etal, J.Electrochem.Soc., Solid State Sci.Techno
l., 130 (6), FMHoulihan et al., Macromolcules, 21, 2001
(1988), European Patent Nos. 0290,750, 046,083, 156,53
No. 5,271,851, 0,388,343, U.S. Pat.
No. 710, No. 4,181,531, JP-A-60-198538, JP-A-53-53
No. 133022, etc., a photoacid generator having an o-nitrobenzyl-type protecting group, M. TUNOOKA et al., Polymer Preprints
Japan, 35 (8), G. Berner et al., J. Rad. Curing, 13 (4), WJM
ijs et al, Coating Technol., 55 (697), 45 (1983), Akzo, H.
Adachi etal, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115
Nos. 0101,122; U.S. Pat.Nos. 618,564; 4,371,605
No. 4,431,774, JP-A-64-18143, JP-A-2-24575
No. 6, iminosulfone described in Japanese Patent Application No. 3-140109, etc.
And disulfone compounds described in JP-A-61-166544 and the like.

Further, a compound in which a group or a compound capable of generating an acid upon irradiation with such a radiation is introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., JA
m. Chem. Soc., 104, 5586 (1982), SPPappas et al., J. Imag.
ing Sci., 30 (5), 218 (1986), S. Kondo et al., Makromol.Ch
em., Rapid Commun., 9, 625 (1988), Y. Yamadaetal, Makrom
ol.Chem., 152, 153, 163 (1972), JVCrivello etal, JP
olymerSci., Polymer Chem.Ed., 17,3845 (1979), U.S. Patent No. 3,849,137, Dokoku Patent No. 3914407, JP-A-63-266
No. 53, JP-A-55-164824, JP-A-62-69263, JP-A-6-69263
3-146038, JP-A-63-163452, JP-A-62-153853
And JP-A-63-146029 can be used.

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

Among the compounds which can be used together and decompose upon irradiation with radiation to generate an acid, those which are particularly effectively used are 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).

[0055]

Embedded image

In the formula, R ¹²⁰¹ is a substituted or unsubstituted aryl group, alkenyl group, and R ¹²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, -C
(Y) Show ₃ . Y represents a chlorine atom or a bromine atom.
Specific examples include the following compounds, but the present invention is not limited thereto.

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

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

[0061]

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 ¹²⁰³ , R ¹²⁰⁴ and R ¹²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents are those having 1 carbon atom for the aryl group.
An alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom. Group.

[0064] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

Further, two of R ¹²⁰³ , R ¹²⁰⁴ and R ¹²⁰⁵ 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.

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

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

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

[0080]

Embedded image

In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ¹²⁰⁶ May be replaced
Represents an unsubstituted alkyl group or aryl group. A is also a substitution
Or unsubstituted alkylene, alkenylene, aryl
Represents a len group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[II] (b) Conductive fine particles or conductive organic polymer (hereinafter also referred to as “component (b)”) The positive resist composition for electron beam or X-ray of the present invention comprises:
It contains at least one member selected from the group consisting of the following substances (1) to (8) (antistatic agents). (1) carbon black or carbon fibers (2) optionally substituted carbon nanotubes (3) polyparaphenylene derivative (4) polythiophene derivative (5) polyparaphenylene vinylene derivative (6) poly N-vinylcarbazole derivative (7 ) Poly (meth) acrylate derivatives having a quaternary ammonium salt structure in the side chain (8) Polystyrene derivatives having a quaternary ammonium salt structure in the side chain

That is, the positive resist composition for electron beam or X-ray of the present invention comprises the conductive fine particles (b-1) of (1) and (2) and the conductive fine particles of (3) to (8). It contains at least one of the organic polymers (b-2). As the conductive fine particles (b-1), furnace black (FT, MT), thermal black (HAF, MA)
F, FEF, SRF, GPF), channel black,
For example, carbon black of a contact method may be used. For the purposes of the present invention, acetylene black is preferred. Further, for the purpose of the present invention, acidic or alkaline carbon black is preferred, and from this viewpoint, acidic channel black and alkaline furnace black are preferred. Further, a channel system is preferable from the viewpoint of preventing the resist from being fogged by light exposure by adding these carbon blacks. Further, those having a small particle size are preferred. HAF, ISAF, MT, GPF
SAF is preferred. As a method for adding these carbon blacks, a master batch method is preferable. As an example, the following are commercially available. These include hydrophilic ones and high-structure ones. ICB (Mitsubishi Chemical) Tire Black I (Mitsubishi Chemical) Ketjen Black EC and Ketjen Black EC
-600JD Harukan XC-72 Seast KH (Tokai Carbon) Seast 9M (Tokai Carbon) AB-12 (Electrochemical Industries, hydrophilic carbon black) Printex 85 (Degussa, volatile matter: 1.0%, specific surface area: 200 m ² / g) ) Special Black 4A (Degussa, volatiles:
(14%, specific surface area: 180 m ² / g) Fine graphite powder is also used. Examples include Systemer PA66 Brate (Showa Denko). In addition, glassy carbon and carbon fiber can also be used. PAN as carbon fiber
System, pitch system, and vapor phase growth system. Also,
Carbon nanotubes and the like are also preferably used. A carbon nanotube is a cylindrical substance obtained by rolling a single layer of graphite (graphine). A cylindrical one-dimensional material composed entirely of carbon atoms has a diameter of about 0.5 nm to 10
It has a helical structure of about nm and a length of about 1 m, and this three-dimensional structure gives quantum properties unique to nanotubes. It is found in soot obtained by arc discharge and can be synthesized by laser evaporation or CVD (chemical vapor deposition). As the addition amount of these carbon black, graphite fine powder, glassy carbon, carbon fiber and carbon nanotube, preferably,
It is 1 to 40% by weight, more preferably 3 to 33% by weight.

The following are specific examples of the conductive organic polymer (b-2).

[0090]

Embedded image

[0091]

Embedded image

The total content of the component (b) is based on the solid content of the positive electrode or X-ray resist composition of the present invention.
Preferably 10 to 60% by weight, more preferably 15 to 5%.
0% by weight.

[III] (c) Resin (c-1) having a group decomposable by an acid and having increased solubility in an alkali developer due to the action of an acid or an alkali-soluble resin having an aromatic ring in a repeating unit Resin (c-2) (Hereinafter,
The electron beam or X-ray positive resist composition of the present invention comprises component (c-1) or (c-
2) can be contained.

[III-1] Resin having an acid-decomposable group and having increased solubility in an alkali developing solution by the action of an acid (c-1) Positive resist composition for electron beam or X-ray of the present invention Things are
A resin (c-1) having a group decomposable by an acid and having increased solubility in an alkali developer by the action of an acid (hereinafter, also referred to as “component (c-1)”), or (d) an acid At least one of low-molecular-weight dissolution inhibiting compounds having a molecular weight of 3000 or less (hereinafter, also referred to as “component (d)”) having a decomposable group and having increased solubility in an alkali developer due to the action of an acid. It is preferred to contain.

As the component (c-1) used in the positive resist composition for electron beam or X-ray of the present invention, the main chain or side chain of the resin, or both of the main chain and side chain, may be used.
It is a resin having a group that can be decomposed by an acid. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable. Preferred groups decomposable with an acid are -COOA ⁰ , -O-
B ⁰ groups, and further containing these groups include -R ⁰ -C
OOA ⁰ or a group represented by -A _r -O-B ⁰ . Where A ⁰ is -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ),
^{Si (R 01) (R 02} ) (R 0 3) or -C (R ⁰⁴⁾
It represents a (R ⁰⁵ ) -OR ⁰⁶ group. B ⁰ is A ⁰ or —CO
Shows a -O-A ⁰ group ^{(R 0, R 01 ~R 06} , and Ar is same meaning as described later).

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

Next, as the base resin when the groups decomposable by these acids are bonded as side chains, -OH or -COOH, preferably -R ⁰ -COOH or -A _r -OH group is added to the side chain. It is an alkali-soluble resin having. For example, an alkali-soluble resin described below can be used.

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

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

Specific examples of the component (c-1) used in the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

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

Weight average molecular weight (Mw) of component (c-1)
Is preferably in the range of 2,000 to 200,000. If the molecular weight is less than 2,000, the film loss is large due to the development of the unexposed portion. If the molecular weight exceeds 200,000, the dissolution rate of the alkali-soluble resin itself in alkali becomes slow and the sensitivity is lowered. More preferably, 5,000 to 10
8,000, more preferably 8,000 to
It is in the range of 50,000. In addition, the molecular weight distribution (Mw /
Mn) is preferably from 1.0 to 4.0, more preferably from 1.0 to 2.0, and particularly preferably from 1.0 to 1.6. The smaller the degree of dispersion, the higher the heat resistance and image forming properties. (Pattern profile, defocus latitude, etc.) becomes good. Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography. Component (c-1) may be used in combination of two or more.

[III-2] The positive resist composition of the present invention comprises, as another component, an alkali-soluble resin (c-2) having an aromatic ring in a repeating unit (hereinafter referred to as “c-2”).
"(C-2) component" or "(c-2) alkali-soluble resin") can be used. That is, in the positive resist composition for electron beam or X-ray of the present invention, as the component (c-2), a resin that is insoluble in water and soluble in an aqueous alkaline solution can be used. When the component (c-2) is used, it is not always necessary to incorporate a resin having a group that is decomposed by the action of the acid as the component (c-1) and increases the solubility in an alkaline developer. Of course,
The combination with the component (c-1) is not excluded. Examples of the (c-2) alkali-soluble resin used in the positive resist composition of the present invention include novolak resins, hydrogenated novolak resins, acetone-pyrogallol resins, 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-2) 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 product of polyhydroxystyrene, styrene-hydroxystyrene copolymer, α -Methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

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 as a mixture of two or more, but are not limited thereto. It is not something to be done.

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. These (c-2) alkali-soluble resins in the present invention may be used in combination of two or more.

[IV] (d) Low molecular weight dissolution inhibiting compound (hereinafter also referred to as “component (d)”) The positive resist composition for electron beam or X-ray of the present invention will be described in detail later (f).
It is preferable to contain the component (d) together with at least one compound selected from a vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound and an aldehyde compound. The component (d) is a low-molecular-weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose solubility in an alkaline developer is increased by the action of an acid. Preferred (d) formulated in the composition of the present invention
The component has at least two groups capable of being decomposed by an acid in its structure.
And a compound having at least eight bonding atoms excluding the acid-decomposable group at the position where the distance between the acid-decomposable groups is farthest. More preferably, the component (d) has at least two groups capable of being decomposed by an acid in its structure, and at a position where the distance between the acid-decomposable groups is farthest away, at least a bonding atom excluding the acid-decomposable group. A compound via at least 10, preferably at least 11, more preferably at least 12, or at least three acid-decomposable groups, and at the position where the distance between the acid-decomposable groups is the longest, an acid-decomposable group Is a compound having at least 9, preferably at least 10, and more preferably at least 11 bonding atoms excluding. The preferred upper limit of the number of bonding atoms is 50,
More preferably, the number is 30. When the low molecular weight dissolution inhibiting compound as the component (d) has three or more, preferably four or more acid-decomposable groups, and even if it has two acid-decomposable groups, the acid-decomposable groups are mutually separated. When they are separated from each other by a certain distance or more, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved. The distance between the acid-decomposable groups is represented by the number of via bond atoms excluding the acid-decomposable groups. For example,
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), the bonding atom is 12 bonding atoms.

[0115]

Embedded image

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

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

Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups are those having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, aralkyloxy groups, acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, and valeryl group. Group, an acyloxy group such as a butyryloxy group, the above alkenyl group, a vinyloxy group.
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group, and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

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

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

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356 and 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.

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

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

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

[0129]

Embedded image

[0130] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ^{15 3} or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,, R ^99, R ¹⁰³ To 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 may be a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogen atom, Group, carboxyl group, cyano group, or -N (R
¹⁵⁵ ) ( ^R156 ) (where ^R155 , ^R156 : H, an alkyl group or an aryl group) ^R110 : a single bond, an alkylene group, or

[0131]

Embedded image

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

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

[0134]

Embedded image

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

[0136]

Embedded image

[0137]

Embedded image

[0138]

Embedded image

[0139]

Embedded image

Specific examples of preferred compound skeletons are shown below.

[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

[0151]

Embedded image

[0152]

Embedded image

[0153]

Embedded image

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

[0155]

Embedded image

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

[V] (f) At least one compound selected from vinyl compounds, cycloalkane compounds, cyclic ether compounds, lactone compounds and aldehyde compounds

The vinyl compound used in the present invention includes vinyl ethers described below, styrene, α-methylstyrene, m-methoxystyrene, p-methoxystyrene,
o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-nitrostyrene, m-nitrostyrene,
p-bromostyrene, 3,4-dichlorostyrene, 2,
Styrenes such as 5-dichlorostyrene and p-dimethylaminostyrene; vinylfurans such as 2-isopropenylfuran, 2-vinylbenzofuran and 2-vinyldibenzofuran; vinyls such as 2-isopropenylthiophene and 2-vinylphenoxatin Thiophenes, N-vinyl carbazoles, vinyl naphthalene, vinyl anthracene,
Acenaphthylene or the like can be used.

Examples of the cycloalkane compound used in the present invention include phenylcyclopropane and spiro [2,4].
Heptane, spiro [2,5] octane, spiro [3,
4] octane, 4-methylspiro [2,5] octane,
Spiro [2,7] decane or the like can be used. As the cyclic ether compound, dioxane such as 4-phenyl-1,3-dioxane, oxetane such as 3,3-bischloromethyloxetane, and compounds such as trioxane and 1,3-dioxepane can be used. Further, glycidyl ethers such as allyl glycidyl ether and phenyl glycidyl ether, glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, bisphenol A type epoxy resins and tetrabromobisphenol A type epoxy resins commercially available under the trade name of Epicoat, Compounds such as bisphenol F type epoxy resin, phenol novolak type epoxy resin, and cresol novolak type epoxy resin can be used.

The lactone compounds used in the present invention include propiolactone, butyrolactone, valerolactone, caprolactone, β-methyl-β-propiolactone, α, α-dimethyl-β-propiolactone, α-methyl- Compounds such as β-propiolactone can be used.

Examples of the aldehyde compound used in the present invention include aliphatic saturated aldehyde compounds such as valeraldehyde, hexanal, heptanal, octanal, nonanal, decanal, cyclohexane carbaldehyde, and phenylacetaldehyde; Aliphatic unsaturated aldehyde compounds such as 2-butenal, 2-butynal and safranal; aromatic aldehyde compounds such as benzaldehyde, tolualdehyde and cinnamaldehyde; tribromoacetaldehyde, 2,2,3-trichlorobutyraldehyde, chlorobenzaldehyde and the like. Halogen-substituted aldehyde compound, glyceraldehyde, aldol, salicylaldehyde, m-hydroxybenzaldehyde, 2,4
-Dihydroxybenzaldehyde, 4-hydroxy-3
Hydroxy- and alkoxy-substituted aldehyde compounds such as methoxybenzaldehyde and piperonal; amino- and nitro-substituted aldehyde compounds such as aminobenzaldehyde and nitrobenzaldehyde; dialdehyde compounds such as succinaldehyde, glutaraldehyde, phthalaldehyde and terephthalaldehyde; phenylglyoxal and benzoyl Ketoaldehyde compounds such as acetaldehyde and derivatives thereof can be used.

Component (f) is preferably a vinyl compound, more preferably a vinyl ether compound, particularly preferably a compound represented by formula (A), in that the effect of the present invention is remarkable. In the general formula (A),
When R _a , R _b and R _c are an aryl group, generally 4-20.
Having an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylmercapto group, an aminoacyl group, a carboalkoxy group, a nitro group, a sulfonyl group, a cyano group or a halogen atom. It may be substituted. Here, examples of the aryl group having 4 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

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

The saturated or olefinically unsaturated ring formed by bonding any two of R _a , R _b and R _c , specifically, cycloalkane or cycloalkene, usually has 3 to 8, Preferably it represents 5 or 6 ring members.

In the present invention, in the general formula (I),
Preferred is an enol ether group in which one of R _a , R _b and R _c is a methyl group or an ethyl group and the remainder is a hydrogen atom, and more preferred is when all of R _a , R _b and R _c are hydrogen. It is a certain general formula [A-1] below.

Formula [A-1] CH ₂ ＣＨCH—O—
R (R: alkyl, substituted alkyl) Here, the alkyl group is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. The substituted alkyl group is a linear, branched or cyclic substituted alkyl group having 1 to 30 carbon atoms.

In the above, examples of the linear, branched or cyclic alkyl group having 1 to 30 carbon atoms include ethyl, linear, branched or cyclic propyl, butyl, pentyl, hexyl, Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Examples include a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, and the like. In the above,
Preferred as a further substituent of the alkyl group is a hydroxy group, an alkyl group, an alkoxy group, an amino group, a nitro group, a halogen atom, a cyano group, an acyl group, an acyloxy group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, An aryl group, an aralkyl group, an imide group, a hydroxymethyl group, -OR ₁₀₀₁ , -C (= O) -R ₁₀₀₂ ,
—OC (＝ O) —R ₁₀₀₃ , —C (＝ O) —O—
R ₁₀₀₄ , -SR ₁₀₀₅ , -C (= S) -R ₁₀₀₆ , -O-
Substituents such as C (= S) -R ₁₀₀₇ and -C (= S) -O-R ₁₀₀₈ are exemplified. Here, R _{1001 to} R ₁₀₀₈ are each independently a linear, branched or cyclic alkyl group, alkoxy group, amino group, nitro group, halogen atom, cyano group, acyl group, sulfonyl group, sulfonyloxy group, sulfonylamino group, an imido _{group, - (CH 2 CH 2 -O} ) n
—R ₁₀₀₉ (where n represents an integer of 1 to 20, R ₁₀₀₉ represents a hydrogen atom or an alkyl group), an aryl group or an aralkyl group which may have a substituent (here, as a substituent Represents a linear, branched or cyclic alkyl group, alkoxy group, amino group, nitro group, halogen atom, cyano group, acyl group, aryl group or aralkyl group.

Preferred examples of the compound represented by formula (A) include, but are not limited to, the following.

[0169]

Embedded image

[0170]

Embedded image

[0171]

Embedded image

As a method for synthesizing the compound represented by the general formula [A-1], for example, Stephen. C. Lapin, Polymers
Paint Color Journal, 179 (4237), 321 (1988), synthesized by reaction of alcohols or phenols with acetylene, or reaction of alcohols or phenols with halogenated alkyl vinyl ether. be able to. It can also be synthesized by reacting a carboxylic acid compound with a halogenated alkyl vinyl ether. The electron beam of the present invention or X
The amount of the compound (f) (preferably, the compound represented by the general formula (A)) in the positive resist composition for a line is preferably 0.5 to 0.5% of the total weight (solid content) of the resist composition.
It is preferably from 50 to 50% by weight, more preferably from 3 to 30% by weight.

Here, examples of the constitution of the positive resist composition for electron beam or X-ray of the present invention are shown below. But,
The content of the present invention is not limited to these. 1) The component (a), the component (b) and the component (c)
-1) A positive resist composition for electron beams or X-rays. 2) The component (a), the component (b), the component (c-
A positive resist composition for electron beam or X-ray, comprising 1) and the above component (d). 3) The component (a), the component (b), the component (c-
A positive resist composition for electron beam or X-ray, comprising 2) and the above component (d). 4) The component (a), the component (b), the component (c-
A positive resist composition for electron beam or X-ray, comprising 1) and the above component (f). 5) The component (a), the component (b), the component (c-
1) A positive resist composition for electron beam or X-ray, comprising the above component (d) and the above component (f). 6) The component (a), the component (b), the component (c-
2) A positive resist composition for electron beam or X-ray containing the above component (d) and the above component (f). In each of the above configuration examples, component (c-1) and component (c
The amount of use in the composition of -2) is preferably 40 to 99% by weight, more preferably 5 to 5% by weight, based on the solid content of the whole composition.
0 to 90% by weight.

The amount of the component (d) used in the composition is 3 to 4 with respect to the solid content of the whole composition in any of the above constitution examples.
Preferably 5% by weight, more preferably 5 to 30% by weight,
More preferably, it is 10 to 20% by weight.

[VI] Other Components The electron beam or X-ray positive resist composition of the present invention may further contain a dye, a pigment, a plasticizer, a surfactant, if necessary.
A photosensitizer, an organic basic compound, a compound having two or more phenolic OH groups for promoting solubility in a developer, and the like can be contained.

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

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

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

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

Preferred organic basic compounds that can be used in the positive resist composition for electron beams or X-rays of 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).

[0181]

Embedded image

Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol,
Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted Or, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-
Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino -4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-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, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.
0] non-5-ene, 2,4,5-triphenylimidal and the like, and among them, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-
Diazabicyclo [4.3.0] non-5-ene, 2,
Examples thereof include 4,5-triphenylimidal and the like, but are not limited thereto.

These nitrogen-containing basic compounds can be used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is usually 0.001 to 10% by weight, based on the solid content of the entire composition in the composition of the present invention.
Preferably it is 0.01 to 5% by weight. If it is less than 0.001% by weight, the effect of the addition cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

The positive resist composition for electron beam or X-ray of the present invention is dissolved in a solvent that dissolves the above-mentioned components, and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate,
Preferred are methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, and the like. These solvents may be used alone or as a mixture. Can be used. In the present invention, as the coating solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monomethyl ether are particularly preferable, whereby the in-plane uniformity is improved. In pursuit of further advances in semiconductors, in addition to performance such as essential high resolution, various factors such as sensitivity, applicability, minimum application amount, adhesion to substrate, heat resistance, storage stability of composition, etc. In view of the above, a high-performance composition is required. Recently, there has been a tendency to create devices using large diameter wafers in order to increase the absolute amount of chips that can be obtained. In particular, in the case of resists for electron beams and X-rays, there is a concern that the throughput may decrease.
The situation of application to fer is increasing. However, if the coating is applied to a large diameter, there is a concern that the coating properties, particularly the in-plane film thickness uniformity, may be reduced. Therefore, it is required to improve the film thickness in-plane uniformity for a large diameter wafer. As a method for confirming the uniformity, the film thickness is measured at many points in the wafer, the standard deviation of each measured value is obtained, and the uniformity can be confirmed by a value three times the standard deviation. It can be said that the smaller this value is, the higher the in-plane uniformity is. As the value, a value three times the standard deviation is preferably 100 or less, more preferably 50 or less.

In addition, a fluorine-based and / or silicon-based surfactant can be used in the positive resist composition for electron beam or X-ray of the present invention. For example, F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florado FC430, 431 (Sumitomo 3M Limited)
Manufactured), Mega Fuck F171, F173, F176, F
189, F08 (Dainippon Ink Co., Ltd.), Surflon S-382, SC-101, 102, 103, 104,
Fluorine-based surfactants such as 105 and 106 (manufactured by Asahi Glass Co., Ltd.) or silicon-based surfactants.
In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant. Surfactants other than fluorine-based and / or silicon-based surfactants can also be used in combination. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether and the like Sorbitan such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; acrylic acid or methacrylic acid (Co) polymerized polyflow no. 75, no. 9
5 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2% by weight or less, preferably 1% by weight or less, based on the solid content of the entire composition in the composition of the present invention. These surfactants may be added alone or in combination of two or more.

The positive resist composition for electron beam or X-ray of the present invention can be dissolved in a solvent and then filtered.
The filter used for this purpose is selected from those used in the field of resist, and specifically, a filter whose material contains polyethylene, nylon or polysulfone is used. More specifically, microguards manufactured by Millipore, microguard plus, microguard minichem-D, microguard minichem-
DPR, Millipore Obtimizer DEV / DEV-
C, Millipore Obturizer 16/14, Ultipore N66 manufactured by Pall Corporation, Posidyne, Nylon Falcon and the like. The pore diameter of the filter can be the one confirmed by the following method. In other words, PSL standard particles (polystyrene latex beads, particle diameter 0.100 μm) are dispersed in ultrapure water, continuously flowed to the primary side of the filter by a tube pump at a constant flow rate, and the challenge concentration is measured by a particle counter. 9
Those that can capture 0% or more can be used as a 0.1 μm pore size filter.

The positive resist composition for electron beams or X-rays of the present invention is applied onto a substrate (eg, silicon / silicon dioxide coating) suitable for use in the production of precision integrated circuit devices by appropriate coating such as spinner or coater. After application by a method, exposure is performed through a predetermined mask, baking and development are performed, whereby a good resist pattern can be obtained.

Examples of the developer for the positive resist composition for electron beam or X-ray of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia. Primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine And quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and alkaline aqueous solutions such as cyclic amines such as pyrrole and piperidine. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

Next, the negative resist composition for electron beam or X-ray of the present invention will be described. The negative resist composition for electron beam or X-ray of the present invention is selected from the group consisting of (a) a compound which generates an acid upon irradiation with an electron beam or X-ray, and (b) conductive fine particles or a conductive organic polymer. At least one selected from the group consisting of (c-2) an alkali-soluble resin having an aromatic ring in the repeating unit, and specifically, an electron beam or an X-ray. Component (a), Component (b) and Component (c-2) in the positive resist composition for use in the present invention.
Is the same as In the negative resist composition for electron beam or X-ray of the present invention, as the component (c-2), at least one of the resins represented by the above general formulas (ca) to (ce) is preferable. .

The resins represented by the general formulas (ca) to (ce) are described in Macromolecules (1995), 25 (11), 3787-3789,
Polym. Bull. (Berlin) (1990), 24 (4), 385-389, using the radical polymerization or living anion polymerization method described in JP-A-8-286375 to polymerize by combining corresponding monomers. Can be synthesized. When a monomer having a hydroxyl group in the molecule is used, it is preferable to protect the hydroxyl group in advance and remove the protective group after polymerization. Also, when protecting with a group that can be decomposed by the action of an acid, a method of introducing a protecting group after the completion of polymer synthesis is generally used.

In the general formulas (ca) to (cd),
_{R 201 ~R 205, R 301 ~R} 305, R 40 1 ~R 405, R 401 ~
R ₄₀₅ each independently represents a hydrogen atom or a methyl group. R
_{206 to} R ₂₁₁ , R _{306 to} R ₃₁₁ , R _{406 to} R ₄₁₁ , R _{506 to} R
The alkyl group or alkoxy group having ₅₁₁ carbon atoms having 1 to 4 carbon atoms may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a t- A butyl group and an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group and a t-butoxy group. The acid-decomposable group for R ₂₁₃ includes a t-butoxycarbonyl group, a t-butoxycarbonylmethyl group, a pyranyl ether group and a —CH
An acetal group represented by (CH ₃ ) —O—R ₂₁₃ can be exemplified, but it is not limited thereto.
(R _{21 3} is 1-8C straight, the branched or cyclic alkyl group (specifically, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, t- butyl group, A cyclohexyl group, etc.), or the following groups.

[0192]

Embedded image

Examples of the acid-decomposable group for R ₂₁₄ include a t-butyl group and the above-mentioned —CH (CH ₃ ) —O—R ₂₁₃ group.

In the general formulas (ca) to (cd),
0 <l ≦ 100, preferably 3 <l ≦ 70, more preferably 5 <l ≦ 50. m, n, o,
For p, 0 ≦ m, n, o, p <100,
Preferably 20 ≦ m, n, o, p ≦ 70, more preferably 30 ≦ m, n, o, p ≦ 50. l + m +
n + o + p = 100

The weight average molecular weight of the resins represented by the general formulas (ca) to (cd) is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the exposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred is 2,000
The range is from 0 to 20,000. In addition, the molecular weight distribution (M
(w / Mn) is preferably from 1.0 to 1.5 (monodisperse polymer) since the development residue is reduced. Here, the weight average molecular weight is defined in terms of polystyrene by gel permeation chromatography.

In the general formula (ce), R ₆₀₁
Represents a hydrogen atom or a methyl group. L represents a divalent linking group. R _f , R _g , R _h , R _i , R _y , and R _z each independently represent a linear, branched, or cyclic alkyl, alkenyl, aryl, or aralkyl group having 1 to 12 carbon atoms. Represents a 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. r, s, t, u, v, w, x represent an integer from 0 to 3, and r + w + x
= 0,1,2,3.

Examples of R _f , R _g , R _h , R _i , R _y , and R _z 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. R
_f, R _y, R _z or R _g, R _h, R _i is Jiakisoru ring-substituted Jiakisoru ring, ethyl substituted Jiakisoru ring, phenyl substituted Jiakisoru ring, dimethyl substituted Jiakisoru ring, to form a dioxane ring preferred.

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

Preferred specific examples of the resin represented by formula (ce) are shown below, but it should not be construed that the invention is limited thereto.

[0200]

Embedded image

[0201]

Embedded image

[0202]

Embedded image

[0203]

Embedded image

The resin represented by the general formula (ce) can be synthesized by a known method such as radical polymerization, cationic polymerization, or anionic polymerization. It is most convenient to carry out the synthesis by radical polymerization of the corresponding monomer. However, depending on the type of the monomer, the synthesis can be carried out more suitably 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.

The resin represented by the general formula (ce) has a molecular weight of more than 3,000 and not more than 1,000,000. Preferably, the weight average molecular weight exceeds 3,000,
500,000 or less. More preferably, the weight average molecular weight is more than 3,000 and not more than 100,000.

The molecular weight distribution (Mw / Mn) of the resin represented by the general formula (ce) is preferably from 1.0 to 1.5, which makes it possible to particularly increase the sensitivity of the resist. it can. The alkali-soluble resin having such a molecular weight distribution can be synthesized by using living anion polymerization in the above synthesis method.

The negative resist composition for electron beam or X-ray of the present invention preferably contains (g) a crosslinking agent which reacts by the action of an acid. (G) a cross-linking agent that reacts by the action of an acid (hereinafter, referred to as “component (g)” or simply as a cross-linking agent)
, A phenol derivative can be used.
Preferably, the molecular weight is 1500 or less, the compound has 1 to 6 benzene rings in the molecule, and further has 2 or more hydroxymethyl groups and / or alkoxymethyl groups in total. Phenol derivatives formed by concentrating on at least one of the benzene rings or binding by distribution are exemplified.

The alkoxymethyl group bonded to the benzene ring preferably has 6 or less carbon atoms. Specifically, methoxymethyl, ethoxymethyl, n-propoxymethyl, i-propoxymethyl, n-butoxymethyl, i-butoxymethyl, sec-butoxymethyl and t-butoxymethyl are preferred. Furthermore, 2-
Alkoxy-substituted alkoxy groups such as methoxyethoxy and 2-methoxy-1-propyl are also preferred. Among these phenol derivatives, particularly preferred ones are listed below.

[0209]

Embedded image

[0210]

Embedded image

[0211]

Embedded image

[0212]

Embedded image

[0213]

Embedded image

[0214]

Embedded image

(In the formula, 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 is A phenol compound having no hydroxymethyl group (compound wherein L ^{1 to} L ⁸ are hydrogen atoms in the above formula) and formaldehyde are reacted 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, Japanese Patent Application Laid-Open Nos.
It can be synthesized by a method described in, for example, Japanese Patent No. 64285.

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.

The phenol derivative having a hydroxymethyl group or an alkoxymethyl group synthesized as described above is preferable in terms of stability during storage, but the phenol derivative having an alkoxymethyl group is preferable from the viewpoint of stability during storage. Particularly preferred. 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.
Also, two or more kinds may be used in combination.

Such a phenol derivative accounts for 3 to 70% by weight, preferably 5 to 5% by weight, of the total solid content of the resist composition.
Used at 0% by weight. When the addition amount of the phenol derivative as a crosslinking agent is less than 3% by weight, the residual film ratio decreases, and when it exceeds 70% by weight, the resolving power decreases,
Further, it is not preferable in terms of stability during storage of the resist solution.

In the negative resist composition for electron beam or X-ray of the present invention, the following other crosslinking agents (i) and (ii) can be used, but it is preferable to use them in combination with the above crosslinking agents. . In this case, the ratio of the other crosslinking agent that can be used in combination with the crosslinking agent of the present invention is 100/0 to 20/80, preferably 90/10 to 40/60, more preferably 80 in molar ratio.
/ 20 to 50/50.

The amount of all the crosslinking agents that can be used in the negative resist composition for electron beam or X-ray of the present invention is 2 to 80% by weight, preferably 5 to 75% by weight, based on the total solid content. Particularly preferably, it is in the range of 10 to 70% by weight.
If the amount of the crosslinking agent is less than 2% by weight, the film loss during development is large, and if it exceeds 80% by weight, it is not preferable from the viewpoint of storage stability.

(I) Compound having N-hydroxymethyl group, N-alkoxymethyl group or N-acyloxymethyl group (ii) Epoxy compound These crosslinking agents will be described in detail below. (i) As a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, European Patent Publication (hereinafter referred to as “EP-A”) No. 0,133,216; West German Patent 3,634,
No. 671, No. 3,711,264, monomer and oligomer-melamine-formaldehyde condensate and urea-formaldehyde condensate, EP-A 0,0
Benzoguanamine-formaldehyde condensate disclosed in the alkoxy-substituted compound disclosed in U.S. Pat. No. 212,482, and the like.

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 Is particularly preferred.

(Ii) The epoxy compound includes monomers, dimers, oligomers, and the like containing one or more epoxy groups.
Polymeric epoxy compounds can be mentioned. 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. Other examples include epoxy resins described and used in U.S. Pat. No. 4,026,705 and British Patent 1,539,192.

Here, examples of the constitution of the negative resist composition for electron beam or X-ray of the present invention include the above-mentioned component (a),
A negative resist composition for electron beam or X-ray containing the component (b), the component (c-2) and the component (g) is exemplified. However, the content of the present invention is not limited to these.

In the above constitutional examples, the amount of the component (a) used in the negative resist composition for electron beam or X-ray is usually 0.1 to 20% by weight based on the solid content of the whole composition.
Further, the content is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight. In each of the above structural examples, the amount of component (b) used in the negative resist composition for electron beam or X-ray is preferably 5 to 30% by weight, more preferably 10 to 30% by weight, based on the solid content of the whole composition. 30% by weight.

In each of the above structural examples, the amount of component (c-2) used in the negative resist composition for electron beams or X-rays is preferably from 10 to 90% by weight based on the solid content of the whole composition. More preferably, it is 15 to 85% by weight. In each of the above constitution examples, the amount of the component (g) used in the negative resist composition for electron beam or X-ray is preferably 30 to 90% by weight, more preferably 50 to 90% by weight, based on the solid content of the whole composition.
~ 80% by weight.

Further, the negative resist composition for electron beam or X-ray of the present invention contains other components such as a surfactant, an organic base compound, and a solvent which can be used for a positive resist composition for electron beam or X-ray. Similarly, it can be contained. The application step of the resist composition and the like can be performed in the same manner as the method described for the positive resist composition for electron beam or X-ray.

[0228]

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.

First, the positive resist composition will be described. "Synthesis of Component (c-1)" [Synthesis of Resin Example (c-21)] 32.4 g (0.2 mol) of p-acetoxystyrene and 7.01 g (0.07 mol) of t-butyl methacrylate were used. Dissolve in 120 ml of butyl acetate, add 0.033 g of azobisisobutyronitrile (AIBN) three times every 2.5 hours at 80 ° C. under a nitrogen stream and stirring, and finally continue stirring for another 5 hours. A polymerization reaction was performed. The reaction solution was hexane 1200
Then, white resin was precipitated. After drying the obtained resin, it was dissolved in 200 ml of methanol. To this, 7.7 g (0.19 mol) of sodium hydroxide / 50 ml of water
Was added thereto and hydrolyzed by heating under reflux for 1 hour. Thereafter, 200 ml of water was added for dilution, and neutralized with hydrochloric acid to precipitate a white resin. This resin was separated by filtration, washed with water and dried. Further tetrahydrofuran 200
The solution was dropped into 5 L of ultrapure water with vigorous stirring and reprecipitated. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain poly (p-hydroxystyrene / t-methacrylic acid t-).
(Butyl) copolymer (c-21).

[Synthesis of Resin Example (c-3)] Poly (p-hydroxystyrene) (VP-8000, manufactured by Nippon Soda Co., Ltd.) 10
g was dissolved in 50 ml of pyridine, and 3.63 g of di-tert-butyl dicarbonate was added dropwise thereto at room temperature with stirring. After stirring at room temperature for 3 hours, 1 L of ion-exchanged water / 20 g of concentrated hydrochloric acid
Was added dropwise to the solution. The precipitated powder was filtered, washed with water, and dried to obtain Resin Example (c-3).

[Synthesis of Resin Example (c-33)] 83.1 g (0.5 mol) of p-cyclohexylphenol was added to 300
dissolved in toluene, 150 g of 2-chloroethyl vinyl ether, 25 g of sodium hydroxide, 5 g of tetrabutylammonium bromide, and 60 g of triethylamine.
g was added and reacted at 120 ° C. for 5 hours. The reaction solution was washed with water, excess chloroethyl vinyl ether and toluene were distilled off, and the obtained oil was purified by distillation under reduced pressure to obtain 4-cyclohexylphenoxyethyl vinyl ether. Poly (p-hydroxystyrene) (V manufactured by Nippon Soda Co., Ltd.)
20 g of P-8000) and 6.5 g of 4-cyclohexylphenoxyethyl vinyl ether were dissolved in 80 ml of THF, and 0.01 g of p-toluenesulfonic acid was added thereto and reacted at room temperature for 18 hours. The reaction solution was added dropwise to 5 L of distilled water with vigorous stirring, and the precipitated powder was filtered and dried to obtain a resin example (c-33).

The resin examples (c-4) and (c-28) were synthesized in the same manner using the corresponding trunk polymer and vinyl ether.

"Synthesis of Component (d)"

[(D) Synthesis Example of Low Molecular Weight Dissolution Inhibiting Compound—
1: Synthesis of compound 41] 1,3,3,5-tetrakis-
44 g of (4-hydroxyphenyl) pentane was added to N, N-
Dissolve in 250 ml of dimethylacetamide, add
Potassium acid 70.7 g, then t-butyl bromoacetate 9
0.3 g was added and the mixture was stirred at 120 ° C. for 7 hours. Reaction mixing
The substance is put into 2 l of ion-exchanged water, and the obtained viscous substance is washed
did. When this is purified by column chromatography
Compound Example 41 (R is all -CH _TwoCOOC_FourH
₉87 g of (t)) were obtained.

[(D) Synthesis Example of Low Molecular Weight Dissolution Inhibiting Compound—
2: Synthesis of compound 43] α, α, α ′, α ′, α ″,
α ",-hexakis (4-hydroxyphenyl) -1,
20 g of 3,5-triethylbenzene was dissolved in 200 ml of N, N-dimethylacetamide, and 28.2 g of potassium carbonate and then 36.0 g of butyl bromoacetate were added thereto, followed by stirring at 120 ° C. for 7 hours. The reaction product was poured into 2 liters of ion-exchanged water, and the obtained viscous material was washed with water.
When this was purified by column chromatography, the above compound example 43 (R was all -CH ₂ COOC ₄ H ₉ (t)) was 3
7 g were obtained.

[Synthesis of Component (f)] [Synthesis Example of Compound Represented by General Formula (A)] (Synthesis of A-22 (benzoyloxyethyl vinyl ether)) 244 g (2 mol) of benzoic acid was added to 3000 parts.
dissolved in toluene and then added with 320 g of 2-chloroethyl vinyl ether.
g, 25 g of tetrabutylammonium bromide and 100 g of triethylamine, and the mixture was heated and stirred at 120 ° C. for 5 hours. The reaction solution was washed with water, and excess 2-chloroethyl vinyl ether and toluene were removed by distillation under reduced pressure. From the obtained oil, 300 g of benzoyloxyethyl vinyl ether as a target substance was obtained by distillation under reduced pressure.

(A-8, A-10, A-12, A-
15, Synthesis of A-18, A-23, A-24 and A-25) In the same manner as in the synthesis of A-22, A-8, A-
10, A-12, A-15, A-18, A-23, A-
24 and A-25 were synthesized.

Examples [Examples and Comparative Examples] (1) Coating of positive resist composition The components shown in the following Table 1 were dissolved in 8.5 g of propylene glycol monomethyl ether acetate, and this was dissolved in 0.1 μm The solution was filtered through a Teflon (registered trademark) filter to prepare a resist solution. Each sample solution was applied on a silicon wafer using a spin coater, and 12
The resist film was dried on a vacuum suction type hot plate at 0 ° C. for 90 seconds to obtain a resist film having a thickness of 0.3 μm.

[0239]

[Table 1]

The acid generator (PA) used as component (a)
G-1, PAG-2) are as follows.

[0241]

Embedded image

Conductive fine particles and conductive organic polymer (cond-a to cond-g) used as component (b)
Is as follows.

[0243]

Embedded image

The composition, physical properties and the like of the component (c-1) used are as follows. (PHS): poly-p-hydroxystyrene (manufactured by Nippon Soda Co., Ltd., trade name: VP-15000) (c-3): p-humanoxystyrene / pt-butoxycarboxystyrene copolymer (molar ratio: 80/2
0), weight average molecular weight 13000, molecular weight distribution (Mw /
Mn) 1.4 (c-4): p-hydroxystyrene / p- (1-ethoxyethoxy) styrene copolymer (molar ratio: 70/3)
0), weight average molecular weight 12000, molecular weight distribution (Mw /
Mn) 1.3 (c-21): p-hydroxystyrene / t-butyl methacrylate copolymer (molar ratio: 70/30), weight average molecular weight 16,000, molecular weight distribution (Mw / Mn) 2.0 (c- 28): p-hydroxystyrene / p- (1-phenethyloxyethoxy) styrene copolymer (molar ratio:
85/15), weight average molecular weight 12000, molecular weight distribution (Mw / Mn) 1.2 (c-33): p-hydroxystyrene / p- (1-phenoxyethoxyethoxy) styrene copolymer (molar ratio: 85 / 15), weight average molecular weight 13000, molecular weight distribution (Mw / Mn) 1.2

(2) Preparation and Evaluation of Resist Pattern An electron beam lithography system (pressing voltage 50 Ke
Irradiation was performed using V). 110 ° C each after irradiation
Heating for 60 seconds with a vacuum adsorption type hot plate,
It was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The cross-sectional shape of the obtained contact hole pattern was observed with a scanning electron microscope.

(3) Evaluation of resolving power The critical resolving power (minimum diameter of hole) in the pattern profile contact hole pattern was defined as the resolving power.

Table 2 shows the results regarding the cross-sectional shape (profile) and resolution of the pattern.

[0248]

[Table 2]

From the results shown in Table 2, it was confirmed that the positive resist compositions of the examples gave a rectangular pattern profile with a high resolution without causing a decrease in sensitivity.

As a result of carrying out in the same manner as in Example (P-1-1) of Table 1 except that the component (b) was Ketjenblack EC-600JD, the resolution was further increased.

A-8, A-10, A-12, A-15, and A-8 have the same configuration as the embodiment (P-1-1) in Table 1.
-18, A-22, A-23, A-24, A-25, p
-Compositions to which methoxystyrene, spirooctane, caprolactone, and terephthalaldehyde were added in an amount of 10% by weight of solid content showed improvements in resolving power and profile shape, respectively.

Further, the same configuration as that of Example (P-1-1) in Table 1 was used, and the surfactant Troisol S-366 was used.
(Manufactured by Troy Chemical Co., Ltd.), Megafac F176 (manufactured by Dainippon Ink Co., Ltd.), Megafac R08 (manufactured by Dainippon Ink Co., Ltd.), polysiloxane polymer KP-341
(Manufactured by Shin-Etsu Chemical Co., Ltd.).
The compositions to which 00 ppm was added showed improvement in the resolving power and profile shape, respectively.

Further, with the same structure as in Example (P-1-1) of Table 1, the organic base compound was changed to 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5 A composition in which -diazabicyclo [4.3.0] non-5-ene, N-cyclohexyl-N'-morpholinoethylthiourea, and 4-dimethylaminopyridine showed similar performance.

Further, in the same configuration as in the above Table 1, the solvent was propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80 /
The composition changed to 20 showed similar performance.

The components shown in Table 1 above were dissolved in the above solvents, and the above Examples (P-1-1) to (P-1-
The composition solution of 18) was filtered through a 0.1 μm polyethylene filter to prepare a resist solution. The in-plane uniformity of each of these resist solutions was evaluated as described below.

(In-plane uniformity) Each resist solution was 8 in.
h. A resist coating film for measuring in-plane uniformity was obtained by coating on a silicon wafer and performing the same processing as the coating of a resist layer as described above. This is a Dainippon Screen Lambd
At aA, the coating film thickness was uniformly measured at 36 locations so as to form a cross along the wafer diameter direction. The standard deviation of each measured value is taken.
Those having a value of 0 or more were evaluated as x. As a result, a solution using propylene glycol monomethyl ether acetate (PGMEA) as a resist coating solvent (Example (P
-1-1) to (P-1-18)) had good in-plane uniformity. Examples (P-1-1) to (P-1-18)
A composition having the same composition as in Example 1 except that the solvent was changed to propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20 also showed similar in-plane uniformity.

(4) Patterning by X-ray Exposure at 1: 1 The Example (P-1-1) and Comparative Example (P-1-101)
Using each of the resist compositions of Comparative Example (P-1-102) and a film thickness of 0.40 in the same manner as in (1) above.
A μm resist film was obtained. Next, patterning was performed in the same manner as in the above (2) except that a 1: 1 X-ray exposure apparatus (gap value: 20 nm) was used, and the resist performance (resolution) was evaluated in the same manner as in the above (3). Table 3 shows the evaluation results.

Table 3 Resist Composition Resolution (μm) Example (P-1-1) 0.06 Comparative Example (P-1-101) 0.10 Comparative Example (P-1-102) 0.10

As is clear from Table 3, it was confirmed that the positive resist compositions of the examples exhibited extremely excellent performance even in X-ray exposure. Therefore, according to the positive resist composition of the example, it has a high resolution, can provide an excellent rectangular pattern profile, and has excellent coatability (in-plane uniformity).

Next, the negative resist composition will be described. "Synthesis of Component (c-2)" [Synthesis of Resin Example (P-1) and Resin Example (P-1 ')]
14.8 g of 5-vinyl-1,3-benzodioxole,
108.1 g of 4-hydroxystyrene is dried in THF 27
After adding to 0 ml, the mixture was heated to 70 ° C. under a nitrogen stream. When the reaction temperature is stabilized, V-601 manufactured by Wako Pure Chemical Industries, Ltd.
Was added 2.5% of the total number of moles of the monomer to start the reaction. After reacting for 6 hours, the reaction mixture was diluted with THF, poured into a large amount of hexane, and precipitated. The powder was collected by filtration, re-precipitated twice in a THF-hexane system, and dried under reduced pressure to obtain a resin (p-1). The weight average molecular weight of the obtained resin was 17,000 in terms of polystyrene as a result of GPC measurement, and the molecular weight dispersity (Mw /
Mn) = 2.15. In the same way as above,
A resin (P-1 ′) having a weight average molecular weight of 10,500 and a molecular weight dispersity of 1.10 was obtained.

[Resin Example (P-2) and Resin Example (P-
Synthesis of 2 ′)] After adding 17.6 g of 3-t-butoxystyrene to 27 g of dry THF, 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 above monomer to start the reaction. 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, reprecipitated and purified twice, dried under reduced pressure (P-
2) was obtained. As a result of GPC measurement, the molecular weight of the obtained resin was 9,800 in terms of polystyrene, and the molecular weight dispersity (Mw / Mn) was 1.66. By the same method as above, a resin (P-2 ′) having a weight average molecular weight of 10,100 and a molecular weight dispersity of 1.12 was obtained.

[Resin Example (P-3) and Resin Example (P-
Synthesis of 3 ′)] A weight-average molecular weight of 13,000 and a molecular weight dispersity of 1 were obtained by the same synthesis method of the resin (P-2) except that 3-t-butoxystyrene was replaced with 4-t-butoxystyrene. .98 resin (P-3) and a resin having a weight average molecular weight of 12,000 and a molecular weight dispersity of 1.15 (P-
3 ′) was obtained.

The resin (P-1), resin (P-1 '), resin (P-2), resin (P-2'), resin (P-3) and resin (P-3 ') are shown below. Show.

[0264]

Embedded image

[Synthesis of Component (g)] [Synthesis of Crosslinking Agent (HM-1)] 1- [α-methyl-α-
(4-hydroxyphenyl) ethyl] -4- [α, α-
Bis (4-hydroxyphenyl) ethyl] benzenene 20
g (Trisp-PA manufactured by Honshu Chemical Industry Co., Ltd.) at 10%
The mixture was added to an aqueous potassium hydroxide solution, stirred and dissolved. Next, while stirring this solution, a 37% formalin aqueous solution 60 m
was gradually added at room temperature over 1 hour. After further stirring at room temperature for 6 hours, the mixture was poured 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 (crosslinking agent (HM-1)) having the following structure. The purity was 92% (liquid chromatography method).

[0266]

Embedded image

[Synthesis of Crosslinking Agent (MM-1)] 20 g of the hydroxymethyl group-containing phenol derivative [HM-1] obtained in the above Synthesis Example was added to 1 liter of methanol, and dissolved by heating with stirring. Next, concentrated sulfuric acid 1
Then, the mixture was refluxed 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. The 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 (crosslinking agent (MM-1)) having the following structure. 90% purity
(Liquid chromatography method).

[0268]

Embedded image

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

[0270]

Embedded image

[0271]

Embedded image

[0272]

Embedded image

Examples [Examples and Comparative Examples] (1) Coating of negative resist composition The components shown in Table 4 below were dissolved in 8.5 g of propylene glycol monomethyl ether acetate, and this was dissolved in 0.1 μm The solution was filtered through a Teflon filter to prepare a resist solution. Each sample solution was applied on a silicon wafer using a spin coater and dried on a vacuum adsorption type hot plate at 120 ° C. for 90 seconds to form a film having a thickness of 0.3 μm.
A μm resist film was obtained.

[0274]

[Table 3]

The acid generator (PA) used as component (a)
G-1, PAG-2), conductive fine particles used as component (b) and conductive organic polymers (cond-a to co-
nd-g) is the same as that used in the positive resist composition.

(2) Preparation of resist pattern and evaluation of resolving power The same procedure as in the case of the positive resist composition was used. Table 5 shows the results regarding the cross-sectional shape (profile) of the pattern and the resolving power.

[Table 4]

From the results shown in Table 5, it was confirmed that the negative-type electron beam resist compositions of Examples had a high resolution and a rectangular pattern profile. At this time, it was confirmed that the sensitivity of the example was comparable to that of the comparative example.

In Example (N-1-1) of Table-4,
As a result of performing the same operation by changing the component (b) to 0.13 g of Ketjen Black EC, the resolution was further increased.

In Example (N-1-1) of Table-4,
The organic base compound was converted to 1,8-diazabicyclo [5.4.
0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, N-cyclohexyl-
The composition changed to N'-morpholinoethylthiourea and 4-dimethylaminopyridine showed the same effect.

In Example (N-1-1) of Table-4,
Surfactant Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), Megafac F176 (Dainippon Ink Co., Ltd.)
), Megafac R08 (Dai Nippon Ink Co., Ltd.),
Compositions to which the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added in an amount of 100 to 300 ppm of the solution composition showed improvements in resolution and profile shape, respectively.

In Example (N-1-1) of Table-4,
Compositions carried out in the same manner except that the crosslinking agents were changed to MM-2 to MM-5 showed the same effects.

In all the examples, the same effect was obtained by changing the solvent to propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20.
Furthermore, in the case of using the compositions of Examples (N-1-1) to (N-1-14) and using an X-ray projector, the effects of the present invention were similarly observed.

Further, the examples (N-1) shown in Table 4 above were used.
-1) to (N-1-16) were filtered through a 0.1 μm polyethylene filter to prepare a resist solution. The in-plane uniformity of each of these resist solutions was evaluated as described below.

(In-plane uniformity) Each resist solution was 8 in.
h. A resist coating film for measuring in-plane uniformity was obtained by coating on a silicon wafer and performing the same processing as the coating of a resist layer as described above. This is a Dainippon Screen Lambd
At aA, the coating film thickness was uniformly measured at 36 locations so as to form a cross along the wafer diameter direction. The standard deviation of each measured value is taken.
Those having a value of 0 or more were evaluated as x. As a result, a solution using propylene glycol monomethyl ether acetate (PGMEA) as a resist coating solvent (Example (N
-1-1) to (N-1-16)) had in-plane uniformity of ○. Examples (N-1-1) to (N-1-16)
A composition having the same composition as in Example 1 except that the solvent was changed to propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20 also showed similar in-plane uniformity.

[0285]

According to the resist composition for an electron beam or X-ray of the present invention, an electron beam or an X-ray having a high resolution and an excellent rectangular pattern profile can be provided without lowering the sensitivity. A resist composition for use. Further, it is possible to provide an electron beam or X-ray resist composition having excellent coatability (in-plane uniformity).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 257/02 C08F 257/02 269/00 269/00 C08K 5/00 C08K 5/00 C08L 101/12 C08L 101/12 G03F 7/004 501 G03F 7/004 501 503 503A 504 504 7/038 601 7/038 601 H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA01 AA02 AA03 AC05 AC06 AD01 AD03 BE00 BG00 CB00 CC03 CC04 CC09 CC10 CC20 FA03 FA17 4J002 AA001 BC022 BC101 BC122 BG052 BQ001 CC042 CE001 CH023 EA028 EA048 EB106 EB108 ED019 ED057 EE018 EE037 EH127 EJ019 EJ049 EL028 EL058 EL087 EV208 EV216 EV206 216 EV216 EB 216 216 4J011 PA22 PA26 PA27 PA45 PA74 PA83 PB27 PC02 QA01 QA09 UA 03 UA04 VA01 WA01 4J026 AA60 AB40 AB46 AC36 BA04 BA05 BA06 BA07 BA08 BA15 BA50 GA07 4J100 AB02R AB07P AB07Q AL03Q AL03R AL08P AL34Q AM07R AM49Q AM49R AQ01P BA02Q BA02R BA03H BA03P BA03QBA03 BC04 BC03 BA04 BA03Q JA38

Claims (14)

[Claims] 1. A composition comprising (a) a compound which generates an acid upon irradiation with an electron beam or X-ray, and (b) at least one selected from the group consisting of conductive fine particles or conductive organic polymers. Or a resist composition for X-rays. 2. The method according to claim 1, wherein (b) the conductive fine particles or the conductive organic polymer is at least one selected from the group consisting of the following substances (1) to (8). The resist composition for electron beam or X-ray according to the above. (1) carbon black or carbon fibers (2) optionally substituted carbon nanotubes (3) polyparaphenylene derivative (4) polythiophene derivative (5) polyparaphenylene vinylene derivative (6) poly N-vinylcarbazole derivative (7 ) Poly (meth) acrylate derivatives having a quaternary ammonium salt structure in the side chain (8) Polystyrene derivatives having a quaternary ammonium salt structure in the side chain (3) at least one compound selected from the group consisting of (a) a compound capable of generating an acid upon irradiation with an electron beam or X-ray and a compound represented by the following general formulas (I) to (III): The positive and negative resist compositions for electron beams or X-rays according to claim 1 or 2, wherein: Embedded image (Wherein, R _{1 to} R ₃₇ are the same or different and are each a hydrogen atom, an alkyl group which may be branched or cyclic, an alkoxy group which may be branched or cyclic, a hydroxy group, a halogen atom Or —S—R ₃₈ group.
₃₈ is an alkyl group which may be branched or cyclic,
Represents an aryl group. Further, at least two or more members out of R _{1 to} R ₃₇ may combine to form a ring containing one or more members selected from a single bond, carbon, oxygen, sulfur and nitrogen. X ^- represents at least one optionally substituted methanesulfonic acid, butanoic acid, octanoic acid, benzenesulfonic acid, an anion of naphthalenesulfonic acid or anthracenesulfonic acid. ) Wherein said general formula (I) ~ (III), X -
Is a linear, branched or cyclic alkyl group substituted by at least one fluorine atom, a linear, branched or cyclic alkoxy group substituted by at least one fluorine atom Acyl group substituted with at least one fluorine atom acyloxy group substituted with at least one fluorine atom sulfonyl group substituted with at least one fluorine atom at least one sulfonyloxy group substituted with at least one fluorine atom Selected from a sulfonylamino group substituted with at least one fluorine atom, an aralkyl group substituted with at least one fluorine atom, and an alkoxycarbonyl group substituted with at least one fluorine atom. Benzenesulfonic acid having at least one of Claim, characterized in that Tarensuruhon acid, or the anion of anthracene sulfonic acid 1-3
The resist composition for electron beam or X-ray according to any one of the above. (D) a low molecular weight dissolution inhibiting compound having a molecular weight of 3,000 or less, which has a group decomposable by the action of an acid and whose solubility in an alkali developing solution is increased by the action of an acid; The resist composition for electron beams or X-rays according to claim 1, wherein 6. A resin selected from the group consisting of (c-1) a resin having a group capable of decomposing under the action of an acid and an aromatic ring in the repeating unit and having increased solubility in an alkali developing solution by the action of an acid. The resist composition for an electron beam or X-ray according to any one of claims 1 to 5, wherein the resist composition contains at least one kind and is of a positive type. 7. A positive type resin comprising: (c-2) at least one selected from the group consisting of an alkali-soluble resin having an aromatic ring in a repeating unit. 5
The resist composition for electron beam or X-ray according to any one of the above. 8. A positive type compound comprising (f) at least one compound selected from the group consisting of a vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound and an aldehyde compound. ~ 7
The resist composition for electron beam or X-ray according to any one of the above. 9. The resist composition for an electron beam or X-ray according to claim 8, wherein the compound (f) is a compound represented by the general formula (A). Embedded image R _a , R _b , R _c ; which may be the same or different, a hydrogen atom,
It represents an alkyl group or an aryl group which may have a substituent, and two of them may combine to form a saturated or olefinically unsaturated ring. R _d represents an alkyl group or a substituted alkyl group. 10. The electron beam or X-ray resist composition according to claim 1, wherein the resist composition is a negative type, which comprises (g) a crosslinking agent which reacts by the action of an acid. 11. The electron beam or X-ray resist composition according to claim 10, wherein (c-2) an alkali-soluble resin having an aromatic ring in the repeating unit is contained. 12. The alkali-soluble resin having an aromatic ring in the repeating unit (c-2) is represented by the following general formula (c-
The resin is at least one selected from the group consisting of resins represented by a) to (ce).
3. The resist composition for electron beam or X-ray according to claim 1. Embedded image In the general formulas (ca) to (cd), R _{201 to} R ₂₀₅ , R _{301 to} R ₃₀₅ , R _{401 to} R ₄₀₅ , and R ₄₀₁ to
R ₄₀₅ each independently represents a hydrogen atom or a methyl group. R
_{206 to} R ₂₁₁ , R _{306 to} R ₃₁₁ , R _{406 to} R ₄₁₁ , R _{506 to} R
₅₁₁ are each independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms, or -OR ₂₁₃ (R ₂₁₃ is
It represents a hydrogen atom or a group that is decomposed by the action of an acid (also referred to as an acid-decomposable group). ). R ₂₁₂ , R ₃₁₂ , R ₄₁₂ , R
₅₁₂ represents —COOR ₂₁₄ (R ₂₁₄ represents a hydrogen atom or an acid-decomposable group). 0 <l ≦ 100 0 ≦ m, n, o, p <100 l + m + n + o + p = 100 In the general formula (ce), R ₆₀₁ represents a hydrogen atom or a methyl group. L represents a divalent linking group. R _f , R _g , R _h , R _i , R _y , and R _z each independently represent a linear, branched, or cyclic alkyl, alkenyl, aryl, or aralkyl group having 1 to 12 carbon atoms. Represents a 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. r, s, t, u, v, w, x represent integers from 0 to 3 and satisfy r + w + x = 0, 1, 2, 3. 13. The method according to claim 1, further comprising (h) a fluorine-based and / or silicon-based surfactant.
3. The resist composition for electron beam or X-ray according to any one of 2. 14. The method according to claim 1, wherein (i) at least one of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate and propylene glycol monomethyl ether is contained as a solvent. Electron beam or X-ray resist composition.