JP2003337414A - Negative resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative resist composition which satisfies such properties as sensitivity, resolving power, variation of sensitivity and line edge roughness when an electron beam or X-rays is used. <P>SOLUTION: The negative resist composition comprises (A) a compound which generates a sulfonic acid upon irradiation with an actinic ray or a radiation, (B) an alkali-soluble resin having a repeating unit having a partial structure represented by a specified formula and (C) a solvent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative resist composition which is suitable for use in ultra-microlithography processes such as production of ultra-LSIs and high-capacity microchips and other photofabrication processes. More specifically, X including the excimer laser light
The present invention relates to a negative resist composition capable of forming a highly precise pattern using an electron beam, an electron beam, etc., and is particularly preferably used for fine processing of a semiconductor element using a high energy beam such as an electron beam or X-ray. The present invention relates to a negative resist composition that can be used.

[0002]

2. Description of the Related Art Integrated circuits are becoming more and more integrated, and in the manufacture of semiconductor substrates such as VLSI, it has become necessary to process ultrafine patterns having a line width of less than half a micron. Came. In order to meet the need, the wavelength of the exposure apparatus used for photolithography has become shorter and shorter, and now far-ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) are being studied. . Furthermore, further finer pattern formation has been studied with electron beams or X-rays.

Electron beams or X-rays are positioned as next-generation or next-generation pattern forming technology, and development of a negative resist capable of achieving high sensitivity, high resolution and rectangular profile shape is desired. Electron beam lithography
The accelerated electron beam releases energy in the process of colliding and scattering with the atoms constituting the resist material to expose the resist material to light. By using a highly accelerated electron beam, the straightness is increased, the influence of electron scattering is reduced, and it is possible to form a rectangular pattern with high resolution, but on the other hand, the electron beam transmittance is increased, The sensitivity will decrease. In this way, in electron beam lithography, there is a trade-off relationship between sensitivity and resolution / resist shape,
The challenge was how to achieve both. X-ray lithography also has the same problem.

Conventionally, various alkali-soluble resins have been proposed for chemically amplified negative resists. JP-A-8-152717 discloses a partially alkyl etherified polyvinylphenol, JP-A-6-67431 and JP-A-1
In 0-10733 publication, a copolymer of vinylphenol and styrene, in patent 2505033 publication is a novolac resin,
JP-A-7-311463, JP-A-8-292559 discloses monodisperse polyvinylphenol, respectively,
These alkali-soluble resins are not compatible with the characteristics of sensitivity, resolution, sensitivity variation rate and line edge roughness under electron beam or X-ray irradiation. Regarding the cross-linking agent, conventionally, methylol melamine, resole resin,
Epoxidized novolac resins, urea resins and the like are used, but these crosslinking agents are unstable to heat and have a problem in storage stability as a resist solution.
The resist compositions proposed in Japanese Patent No. 3000740, JP-A-9-166870, and JP-A-2-15270 also show sensitivity under electron beam or X-ray irradiation, resolution, sensitivity variation rate, and line edge roughness. It was not possible to sufficiently satisfy the characteristics of. Here, the line edge roughness means that the top and bottom edges of the resist line pattern randomly fluctuate in the direction perpendicular to the line direction due to the characteristics of the resist. Sometimes the edges look uneven.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the problems of the technique for improving the performance of microfabrication, which uses actinic rays or radiation, and particularly to use electron beams or X-rays. On the other hand, it is to provide a chemically amplified negative resist composition satisfying the characteristics of sensitivity, resolution, sensitivity variation and line edge roughness.

[0006]

The present invention is as follows.

(1) (A) a compound capable of generating a sulfonic acid upon irradiation with actinic rays or radiation, (B) an alkali-soluble resin containing a repeating unit having a partial structure represented by the following general formula (1), and ( C) A negative resist composition containing a solvent.

[0008]

[Chemical 3]

In the formula (1), R is a single bond or a divalent linkage.
Represents a group. R₁, R₂, R₃, R_Four, R _FiveAre each independently
It represents a substituent or a group represented by the following general formula (2). However
R₁, R₂, R₃, R_Four, R_FiveAt least one is one of the following
It represents a group represented by general formula (2).

[0010]

[Chemical 4]

In the formula (2), R ₆ and R ₇ each independently represent a hydrogen atom or an alkyl group. In addition, R ₆ and R ₇ may combine to form a ring. R ₈ is a hydrogen atom, acetyl group, t
-Represents a butoxycarbonyl group or an alkyl group.

(2) The negative resist composition as described in (1) above, which further comprises (D) an organic basic compound.

The preferred embodiments of the present invention will be described below. (3) A step of forming a film containing the composition according to (1) or (2), a step of irradiating the film with a radiation having a desired pattern, and developing the film with an alkaline developer. And a step of forming a negative pattern.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds constituting the negative resist composition of the present invention will be described below.

[1] (B) Alkali-soluble resin containing a repeating unit having a partial structure represented by the above general formula (1) (hereinafter, also referred to as (B) alkali-soluble resin, (B) component) The alkali-soluble resin in is a resin that is insoluble in water and soluble in an alkaline aqueous solution (also referred to as an alkali-soluble resin). The alkali dissolution rate of the alkali-soluble resin was measured with 0.261N tetramethylammonium hydroxide (TMAH) (23
C.) and 20 liters / second or more are preferable. It is particularly preferably 200 Å / sec or more (Å is angstrom).

The alkali-soluble resin (B) of the present invention contains a repeating unit having a group represented by the following general formula (1) as a partial structure.

[0017]

[Chemical 5]

In the formula (1), R is a single bond or a divalent linkage.
Represents a group. R₁, R₂, R₃, R_Four, R _FiveAre each independently
It represents a substituent or a group represented by the following general formula (2). However
R₁, R₂, R₃, R_Four, R_FiveAt least one is one of the following
It represents a group represented by general formula (2).

[0019]

[Chemical 6]

In the formula (2), R ₆ and R ₇ each independently represent a hydrogen atom or an alkyl group. In addition, R ₆ and R ₇ may combine to form a ring. R ₈ is a hydrogen atom, acetyl group, t
-Represents a butoxycarbonyl group or an alkyl group.

Examples of the divalent linking group of R include, for example,
_{-CH 2 -, - COO -,} - COOCH 2 -, - OCH 2
_{CH 2 O -, - OCH 2} -, and -CONH-, and the like. The substituents of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are:
For example, hydrogen atom, alkyl group (may be linear, branched or cyclic, preferably having 1 to 6 carbon atoms), alkoxy group (may be linear, branched or cyclic, preferably having 1 to 5 carbon atoms) , Acetoxy group, hydroxyl group, thiol group and the like. Specific examples of the substituent include, for example, hydrogen atom, hydroxyl group, thiol group, methyl group, ethyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, Cyclopentyl group, cyclohexyl group, methoxy group, ethoxy group, isopropyloxy group, n-butoxy group, isobutyloxy group, t-butyloxy group, pentyloxy group,
Examples include neopentyloxy group and acetoxy group. R
_At least two members out of _{1 to} R ₅ may combine to form a ring, and specific examples of the ring to be formed include a dioxole ring, a methyl-substituted dioxole ring, an ethyl-substituted dioxole ring,
Examples thereof include a phenyl-substituted dioxole ring, a dimethyl-substituted dioxole ring, and a dioxane ring. As the substituent, preferably a hydrogen atom, a hydroxyl group, a methyl group,
A methoxy group, an ethoxy group, and a dioxole ring.

Specific examples of the alkyl group represented by R ₆ and R ₇ include those having 1 to 8 carbon atoms, which may be linear, branched or cyclic, and include, for example, methyl group, ethyl group, isopropyl group, Examples thereof include n-butyl group, isobutyl group, t-butyl group, cyclopentyl group and cyclohexyl group. R ₆ and R ₇ may combine to form a ring, and examples of the ring formed include a cyclopentyl ring and a cyclohexyl ring. R ₆ and R ₇ are preferably a methyl group, an ethyl group, a cyclohexyl group, or a cyclohexyl ring formed by combining R ₆ and R ₇ .

Specific examples of the alkyl group for R ₈ include
It has 1 to 8 carbon atoms, and may be linear, branched or cyclic, and includes, for example, methyl group, ethyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, Examples thereof include a hexyl group, a cyclopentyl group and a cyclohexyl group. R ₈ is preferably a hydrogen atom, an acetyl group, a t-butoxycarbonyl group or a methyl group.

Specific examples of the repeating unit having the partial structure represented by the above general formula (1) are the same as those described in the specific examples of the alkali-soluble resin (B) described later, but are not limited thereto. Not something.

The alkali-soluble resin (B) used in the present invention may contain a repeating unit other than the repeating unit having the partial structure represented by the general formula (1).

Other repeating units include, for example, styrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, vinylnaphthalene and α-.
Examples thereof include methylstyrene, α-methyl-o-hydroxystyrene, α-methyl-m-hydroxystyrene, α-methyl-p-hydroxystyrene, α-methylvinylnaphthalene and the like.

The (B) alkali-soluble resin used in the present invention contains the repeating unit represented by the general formula (1) in an amount of generally 1 to 100 mol%, preferably 5 to 100 mol%.
Particularly preferably, the content is 10 to 100 mol%.

Due to the action of sulfonic acid, (B) alkali
Mechanism of soluble resin becoming insoluble in alkaline aqueous solution
To R₆, R₇Is a methyl group, R₈When is a hydrogen atom
It is presumed as follows. That is, sulfone
A dehydration reaction occurs due to the action of acid to generate a tertiary cation.
And R ₆, R₇Because the hydrogen atom on carbon is abstracted
A double bond is formed, or a double bond is formed on the tertiary cation.
Crosslinks are formed by the nuclear reaction. The former
In some cases, insolubility in alkaline aqueous solution due to polarity conversion
And in the latter case due to cross-linking
Due to the formation of molecules,
It is estimated that solubilization will occur.

The alkali-soluble resin (B) in the present invention can be synthesized by a known method such as radical polymerization, cationic polymerization or anionic polymerization. It is easiest to perform radical polymerization by combining the corresponding monomers,
Depending on the monomer, it can be synthesized more suitably when cationic polymerization or anionic polymerization is used. Further, when the monomer causes a reaction other than the polymerization depending on the polymerization initiation species,
A desired polymer can be obtained by polymerizing a monomer into which an appropriate protecting group has been introduced, and deprotecting after the polymerization.
Further, regarding a polymer having alkoxy, a desired polymer can be obtained also by subjecting a hydroxyl group of a polymer having a corresponding hydroxyl group to an etherification reaction. The polymerization method is described in Experimental Chemistry Course 28, Polymer Synthesis, New Experimental Chemistry Course 19, Polymer Chemistry [I] and the like.

The alkali-soluble resin (B) of the present invention has a molecular weight of more than 2,000 and 1,000,000 or less. The weight average molecular weight is preferably more than 2,000 and 500,000 or less. More preferably, the weight average molecular weight is more than 2,000 and 100,000 or less.

The molecular weight distribution (Mw / Mn) of the alkali-soluble resin (B) which can be synthesized by the above-mentioned synthetic method is 1.
It is preferably from 0 to 1.5, which makes it possible to enhance the sensitivity of the resist. The alkali-soluble resin having such a molecular weight distribution can be synthesized by utilizing living anionic polymerization in the above synthesis method.

Specific examples of the (B) alkali-soluble resin of the present invention are shown below, but the invention is not limited thereto. Further, the repeating unit ratio, the weight average molecular weight, and the dispersity are also shown, but the present invention is not limited to these.

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

In the present invention, other alkali-soluble resin may be used in combination. Examples of the other alkali-soluble resin used in the present invention include novolac resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-
Polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p- Hydroxystyrene copolymer, partial O-alkylated product with respect to hydroxyl groups of polyhydroxystyrene (for example, 5 to 30 mol% 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 methacrylic acid Examples thereof include, but are not limited to, resins and derivatives thereof.

Other particularly preferred alkali-soluble resins are
Novolac resin and o-polyhydroxystyrene, m-
Polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partial O-alkylation of polyhydroxystyrene, or O-acylated product, styrene-hydroxystyrene copolymer, α-methyl It is a styrene-hydroxystyrene copolymer. The novolac resin is obtained by addition-condensing the following predetermined monomers as main components with aldehydes in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
-Cresol, p-cresol, o-cresol and other cresols, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol and other xylenols, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2 -Methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, alkoxyphenols such as p-butoxyphenol, 2-methyl-4-isopropyl Feno Bis-alkylphenols etc., m
-Hydroxy aromatic compounds such as chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or in combination of two or more, but are not limited thereto. Not something that is done.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde and β-.
Phenylpropyl aldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o -Methylbenzaldehyde, m-methylbenzaldehyde,
Although p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde and acetals thereof such as chloroacetaldehyde diethyl acetal can be used, formaldehyde is used among them. Is preferred. These aldehydes may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or 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 irradiated portion after development is large, and if it exceeds 30,000, the developing speed becomes small. Especially preferred is 2,000 to 20,0.
The range is 00. The weight average molecular weight of the polyhydroxystyrene other than the novolac resin, its derivative, and the copolymer is 2000 or more, preferably 2000 to
It is 30,000, more preferably 2,000 to 20,000. Here, the weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography.

These alkali-soluble resins in the present invention may be used as a mixture of two or more kinds.

The amount of the alkali-soluble resin having the repeating unit represented by the general formula (1), which is a characteristic component of the present invention, is 5 to 5 based on the total weight of the resist composition (excluding the solvent).
90% by weight, preferably 6-80% by weight. Even when another alkali-soluble resin is used in combination, the total amount of the alkali-soluble resin including the alkali-soluble resin having the repeating unit of the general formula (1) is based on the total weight of the resist composition (excluding the solvent). , Usually 5 to 90% by weight, preferably 6 to 80% by weight.

[2] (A) Compound that Generates Sulfonic Acid upon Irradiation with Actinic Rays or Radiation (hereinafter, also referred to as "(A) Acid Generator" or "(A) Component") Used in the present invention ( A) The acid generator is a compound that generates a sulfonic acid upon irradiation with actinic rays or radiation, and is a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photobleaching agent for dyes, and a photochromic agent. , Or known light used for micro resists (400-200 nm ultraviolet light, deep ultraviolet light (g line, h line, i line, KrF excimer laser light)), ArF excimer laser light, electron beam, X-ray, It can be appropriately selected and used among the compounds which generate a sulfonic acid by a molecular beam or an ion beam and mixtures thereof.

Also used in the present invention (A).
Examples of the acid generator include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, onium salts, organic halogen compounds, organic metal / organic halides, and o-nitrobenzyl type protecting groups. Examples thereof include acid generators having an acid, compounds such as iminosulfonates that photolyze to generate sulfonic acids, disulfone compounds, diazoketosulfones, and diazodisulfone compounds. Further, a group in which these acid generating groups or compounds are introduced into the main chain or side chain of the polymer can be used.

Further, VNR Villai, Synthesis, (1), 1 (198
0), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971),
Compounds generating an acid described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), US Pat. No. 3,779,778, and European Patent 126,712 can also be used.

Among the above-mentioned (A) acid generators, an acid generator whose anion has a fluorine atom is mentioned as an example of one that is particularly effectively used. For example, the cation portion is composed of iodonium or sulfonium, anionic part R ^F SO ₃ ^- (wherein, the R ^F is, a fluorine-substituted alkyl group having 1 to 10 carbon atoms) composed of anions represented by An acid generator selected from known sulfonates is used. The fluorine-substituted alkyl group represented by R ^F may be linear, branched or cyclic. Preferred R ^F is a fluorine-substituted linear alkyl group represented by CF ₃ (CF ₂ ) y, where y is an integer of 0 to 9. Examples of the effective (A) acid generator include those having an anion moiety of aromatic sulfonate anion such as pentafluorobenzene sulfonate anion and condensed polynuclear aromatic sulfonate anion such as naphthalene-1-sulfonate anion. You can

The cation part of the acid generator is preferably represented by the following general formulas (I) to (III).

[0050]

[Chemical 12]

In the above general formulas (I) to (III), R ₁
To R ₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom or —SR.
Represents ₃₈ units. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. R ₁ ~ R ₁₅ , R ₁₆ ~
Two or more of R ₂₇ and R _{28 to} R ₃₇ are combined to form a ring containing one or more selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom. Good.

In the general formulas (I) to (III), R _{1 to} R
_As the linear or branched alkyl group of ₃₈ , a carbon number such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, or a t-butyl group, which may have a substituent. One to four can be mentioned. Examples of the cyclic alkyl group include those having a carbon number of 3 to 8, such as cyclopropyl group, cyclopentyl group and cyclohexyl group, which may have a substituent. Examples of the linear or branched alkoxy group for R _{1 to} R ₃₇ include a methoxy group, an ethoxy group,
Examples thereof include those having 1 to 4 carbon atoms such as hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group. Examples of the cyclic alkoxy group include a cyclopentyloxy group, for example, a cyclopentyloxy group and a cyclohexyloxy group.

Examples of the halogen atom represented by R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group of 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. These substituents preferably have 1 to 1 carbon atoms.
4 alkoxy groups, halogen atom (fluorine atom, chlorine atom, iodine atom), aryl group having 6 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, cyano group, hydroxy group, carboxy group, alkoxycarbonyl Group, nitro group and the like.

Further, R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , R _{28 to} R
Of ₃₇ , one or two selected from a single bond, carbon, oxygen, sulfur, and nitrogen, which is formed by combining two or more.
Examples of the ring containing at least one kind include a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, and a pyrrole ring.

Specific examples of the acid generator (A) that can be used in the present invention are shown below.

[0056]

[Chemical 13]

[0057]

[Chemical 14]

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

[0062]

[Chemical 19]

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

[0066]

[Chemical formula 23]

[0067]

[Chemical formula 24]

[0068]

[Chemical 25]

[0069]

[Chemical formula 26]

[0070]

[Chemical 27]

[0071]

[Chemical 28]

[0072]

[Chemical 29]

[0073]

[Chemical 30]

[0074]

[Chemical 31]

[0075]

[Chemical 32]

[0076]

[Chemical 33]

[0077]

[Chemical 34]

Further, the following acid generators can be preferably used.

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

[0080]

[Chemical 35]

In the formula, R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. However, at least one of R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ is not an aryl group. Z ⁻ represents a counter anion, for example, perfluoroalkane sulfonate anion such as CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonate anion, condensed polynuclear aromatic sulfonate anion such as naphthalene-1-sulfonate anion, anthraquinone sulfone. Examples thereof include acid anions and sulfonic acid group-containing dyes, but are not limited thereto.

Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ may be bonded to each other via a single bond or a substituent. Specific examples include the compounds shown below,
It is not limited to these.

[0083]

[Chemical 36]

[0084]

[Chemical 37]

[0085]

[Chemical 38]

[0086]

[Chemical Formula 39]

The onium salt represented by the general formula (PAG4) is known, and can be synthesized by the method described in, for example, US Pat. Nos. 2,807,648 and 4,247,473 and JP-A-53-101,331.

(2) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

[0089]

[Chemical 40]

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0091]

[Chemical 41]

[0092]

[Chemical 42]

[0093]

[Chemical 43]

[0094]

[Chemical 44]

[0095]

[Chemical formula 45]

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

[0097]

[Chemical formula 46]

Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group.

Specific examples include, but are not limited to, the compounds shown below.

[0100]

[Chemical 47]

In the present invention, the acid generator (A) may be used in combination with an acid generator capable of generating an acid other than sulfonic acid upon irradiation with actinic rays or radiation. Examples of the acid generator that generates an acid other than sulfonic acid include, for example, the cation portion represented by the general formulas (I) to (III) and the anion portion BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ^- , Si
Compounds which are inorganic anions such as F ₆ ²⁻ , CIO ₄ ⁻ or carboxylate anions and compounds represented by the above general formula (PAG4), in which the Z ⁻ counter anion is BF ₄ ⁻ , As
Examples thereof include compounds that are inorganic anions such as F ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , CIO ₄ ^{− and the} like, or carboxylate anions.

Specific preferred examples of the acid generator which generates an acid other than sulfonic acid are shown below, but the present invention is not limited thereto.

[0103]

[Chemical 48]

[0104]

[Chemical 49]

[0105]

[Chemical 50]

[0106]

[Chemical 51]

[0107]

[Chemical 52]

The amount of the acid generator (A) added is usually in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, and more preferably based on the solid content in the composition. Is used in the range of 0.1 to 15% by weight.
If the amount of the acid generator (A) added is less than 0.001% by weight, the sensitivity is lowered, and if the amount added is more than 40% by weight, the profile is deteriorated and the process (especially bake) margin is narrowed, which is not preferable. .

[3] (D) Organic Basic Compound The preferred organic basic compound that can be used in the present invention is a compound having a stronger basicity than phenol. Of these, nitrogen-containing basic compounds are preferable. As a preferable chemical environment, the structures of the following formulas (A) to (E) can be mentioned.

[0110]

[Chemical 53]

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or 1 carbon atom. ~ 6 hydroxyalkyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R is
²⁵¹ and R ²⁵² may combine with each other to form a ring.
R ^<253> , R ^<254> , R ^<255> and R ^{<256>, which} may be the same or different, each represents an alkyl group having 1 to 6 carbon atoms.

More preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferably a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. And a compound having an alkylamino group.

Specific preferred examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, imidazole, Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted Alternatively, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group. Is.

Particularly preferred compounds are guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2 , 4,5-Triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2
-(Aminomethyl) pyridine, 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-amino Ethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole,
5-amino-3-methyl-1-p-tolylpyrazole,
Pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6
-Dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine and the like, but not limited thereto.

These organic basic compounds may be used alone or in combination of two or more. The ratio of the acid generator (A) and the organic basic compound (D) used in the composition is
It is preferable that ((A) acid generator) / ((D) organic basic compound) (molar ratio) = 2.5 to 300. If the molar ratio is less than 2.5, the sensitivity may be low and the resolution may be lowered. If the molar ratio is more than 300, the resist pattern may be thickened with the lapse of time after the irradiation and the heat treatment, and the resolution may be lowered. . ((A) Acid generator)) /
The ((D) organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

[4] (C) Solvents The negative resist composition of the present invention is dissolved in a solvent that dissolves each of the above components and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate. , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide , Dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents may be used alone. Rui is used as a mixture. A particularly preferred solvent is
It is a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether.

[5] Crosslinking Agent A compound which can be used in the present invention and which is crosslinked by an acid (hereinafter, appropriately referred to as an acid crosslinking agent or simply a crosslinking agent) is
A compound capable of cross-linking an alkali-soluble resin in the presence of an acid, for example, an acid generated by irradiation with radiation. Examples of such a cross-linking agent include compounds having one or more kinds of substituents (hereinafter referred to as "cross-linkable substituents") having cross-linking reactivity with an alkali-soluble resin.

Specific examples of such crosslinkable substituents include (i) hydroxyalkyl groups such as hydroxyalkyl groups, alkoxyalkyl groups and acetoxyalkyl groups or derivatives thereof; (ii) formyl groups, carboxyalkyl groups, etc. A carbonyl group or a derivative thereof; (iii) a nitrogen-containing group-containing substituent such as a dimethylaminomethyl group, a diethylaminomethyl group, a dimethylolaminomethyl group, a diethylolaminomethyl group, a morpholinomethyl group; (iv) a glycidyl ether group, Glycidyl ester group,
Glycidyl group-containing substituents such as glycidylamino group; (v) Allyloxyalkyl groups such as benzyloxymethyl group, benzoyloxymethyl group, aromatic derivatives such as aralkyloxyalkyl groups; (vi) Vinyl group, isopropenyl group And a polymerizable multiple bond-containing substituent such as As the crosslinkable substituent of the crosslinking agent of the present invention, a hydroxyalkyl group, an alkoxyalkyl group and the like are preferable, and an alkoxymethyl group is particularly preferable.

Examples of the crosslinking agent having a crosslinkable substituent include (i) a methylol group-containing melamine compound, a methylol group-containing benzoguanamine compound, a methylol group-containing urea compound, a methylol group-containing glycoluril compound, and a methylol group-containing phenol compound. (Ii) Alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds and the like. Compound (iii) Carboxymethyl group-containing melamine compound, Carboxymethyl group-containing benzoguanamine compound, Carboxymethyl group-containing urea compound, Carboxymethyl group Carboxymethyl group-containing compounds such as contained glycoluril compounds and carboxymethyl group-containing phenol compounds; (iv) Bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resole resin epoxy Examples thereof include compounds and epoxy compounds such as poly (hydroxystyrene) -based epoxy compounds.

As the cross-linking agent, a resin in which the cross-linking substituent is introduced into the acidic functional group in the alkali-soluble resin to give the property as a cross-linking agent can be used. In that case, the introduction rate of the crosslinkable substituent is usually 5 to 60 mol%, preferably 10 to 50 mol%, and more preferably 1 with respect to the total acidic functional groups in the alkali-soluble resin.
It is adjusted to 5 to 40 mol%. When the introduction rate of the crosslinkable substituent is less than 5 mol%, it becomes difficult to cause a sufficient cross-linking reaction, the remaining film rate is lowered, and the pattern swelling phenomenon and meandering are likely to occur. Then, the alkali solubility of the alkali-soluble resin is lowered, and the developability tends to deteriorate.

In the resist composition of the present invention, the crosslinking agent is an alkoxymethyl urea compound or its resin,
Alternatively, an alkoxymethylated glycoluril compound or a resin thereof is preferable. Examples of the particularly preferable crosslinking agent (B1) include compounds represented by the following (2) to (4) and alkoxymethylated melamine compounds.

[0122]

[Chemical 54]

R ₅ in formulas (2) to (4) are each independently a hydrogen atom, an alkyl group (having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group). ) Or an acyl group (preferably having 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, for example, an acetyl group or a propionyl group). R _{6 to} R ₉ in formula (2) are each independently a hydrogen atom, a hydroxyl group, an alkyl group (preferably having a carbon number of 1 to 5, more preferably a carbon number of 1 to 3, for example, a methyl group, an ethyl group, a propyl group). ) Or an alkoxyl group (preferably having a carbon number of 1 to 5, more preferably a carbon number of 1 to 3, for example, a methoxy group, an ethoxy group, a propoxy group). X represents a single bond, a methylene group or an oxygen atom. X
Is preferably a single bond or a methylene group. In addition, these groups may further have a substituent such as an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a hydroxyl group and a halogen atom.

Specific examples of the compounds represented by the formulas (2) to (4) and the alkoxymethylated melamine compound are shown below, but the invention is not limited thereto.

[0125]

[Chemical 55]

[0126]

[Chemical 56]

The cross-linking agent, for example, undergoes a condensation reaction of a urea compound or a glycoluril compound with formalin to introduce a methylol group, and then is etherified with a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol or butyl alcohol, Then, the reaction liquid is cooled to obtain a compound or a resin thereof which precipitates and is obtained. The cross-linking agent is CYMEL (trade name, manufactured by Mitsui Cyanamid), Nicalad (manufactured by Sanwa Chemical)
It is also available as a commercial product such as.

Further, as a particularly preferable cross-linking agent (B2), a phenol derivative having 1 to 6 benzene rings in the molecule, and two or more hydroxymethyl groups and / or alkoxymethyl groups in the whole molecule are further included. However, a compound in which it is bonded to at least one of the benzene rings can be mentioned. Preferably, the molecular weight is 1500
Hereinafter, it has 1 to 6 benzene rings in the molecule, and further has 2 or more hydroxymethyl groups and / or alkoxymethyl groups in total, and at least one of the hydroxymethyl groups and alkoxymethyl groups Examples of the phenol derivative are those which are concentrated in the benzene ring of or are distributed by being distributed.

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

[0130]

[Chemical 57]

[0131]

[Chemical 58]

[0132]

[Chemical 59]

[0133]

[Chemical 60]

[0134]

[Chemical formula 61]

[0135]

[Chemical formula 62]

(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.) The phenol derivative having a hydroxymethyl group corresponds to It can be obtained by reacting a phenol compound having no hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde under a base catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, JP-A-6-282067 and JP-A-7-
It can be synthesized by the method described in Japanese Patent No. 64285.

The phenol derivative having an alkoxymethyl group can be obtained by reacting the corresponding phenol derivative having a hydroxymethyl group with an alcohol under an acid catalyst. At this time, in order to prevent resinification and gelation, it is preferable to carry out the reaction at a temperature of 100 ° C. or lower. Specifically, it can be synthesized by the method described in European Patent EP632003A1 and the like.

The phenol derivative having a hydroxymethyl group or an alkoxymethyl group thus synthesized is preferable from the viewpoint 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, which are concentrated in any of the benzene rings, or which are bonded by distributing, may be used alone,
Moreover, you may use it in combination of 2 or more type.

In the present invention, the crosslinking agent is used in an amount of 3 to 70% by weight, preferably 5 to 50% by weight, based on the total solid content of the resist composition. If the amount of the cross-linking agent added is less than 3% by weight, the residual film rate will decrease, and if it exceeds 70% by weight, the resolution will decrease, and it will be less preferable in terms of stability during storage of the resist solution.

Two or more kinds of the above-mentioned compound having an N-hydroxymethyl group, N-alkoxymethyl group or N-acyloxymethyl group and the phenol derivative having a hydroxymethyl group or an alkoxymethyl group may be used in combination. .

[6] Other Components Used in the Composition of the Present Invention The negative resist composition of the present invention may further contain a dye, a surfactant and the like, if necessary.

[6] -1 Dyes Suitable dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 1
03, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-5.
05 (all manufactured by Orient Chemical Industry Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170).
B), malachite green (CI42000), methylene blue (CI52015) and the like.

[6] -2 Surfactants The negative resist composition of the present invention may preferably contain a fluorine-based and / or silicon-containing surfactant. The negative resist composition of the present invention preferably contains one or more of a fluorine-based surfactant, a silicon-based surfactant and a surfactant containing both a fluorine atom and a silicon atom. . When the negative resist composition of the present invention contains the above components together with the above surfactant, it is particularly effective when the line width of the pattern is narrower, and the development defects are further improved. Examples of these surfactants include, for example, JP-A-62-36663 and JP-A-61-2.
26746, JP 61-226745, JP 62-170950, JP 63-34540, JP 7-230165, JP 8-62834
No. 9-54432, No. 9-5988, U.S. Pat.
No. 20, No. 5360692, No. 5529881, No. 5296330, No. 543
Examples thereof include the surfactants described in Nos. 6098, 5576143, 5294511 and 5284451, and the following commercially available surfactants can be used as they are. Examples of commercially available surfactants that can be used include Ftop EF301, EF303, (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Ltd.), Megafac F171, F173, F176, F189, R08.
(Manufactured by Dainippon Ink and Chemicals, Inc.), Surflon S-382, SC10
1, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), and other fluorine-based surfactants or silicon-based surfactants. Further, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The content of the above-mentioned surfactant is usually 0.001% by weight to 2 based on the solid content in the composition of the present invention.
%, Preferably 0.01% to 1% by weight.
These surfactants may be added alone, or
It can also be added in several combinations.

Specific examples of the surfactants that can be used in addition to the above include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and the like. Polyoxyethylene alkyl allyl ethers such as ethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostea Sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene Nonionics such as polyoxyethylene sorbitan fatty acid esters such as rubitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Examples thereof include system surfactants. The amount of these other surfactants to be added is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solid content in the composition of the present invention.

In the process of forming a pattern on the resist film in the production of precision integrated circuit devices, etc., the negative of the present invention is formed on the substrate (eg, silicon / silicon dioxide covering, glass substrate, transparent substrate such as ITO substrate). A good resist pattern can be formed by applying a mold resist composition and then irradiating it with an actinic ray or radiation drawing device, followed by heating, developing, rinsing and drying. In the present invention, as actinic rays or radiation, 254 to 15
Examples thereof include 7 nm deep ultraviolet ray or excimer laser, X-ray or electron beam, and electron beam or X-ray is preferable.

As the developing solution applied to the negative resist composition of the present invention, sodium hydroxide, potassium hydroxide,
Inorganic alkalis such as 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, triethylamine and methyldiethylamine. Tertiary amines such as
Aqueous solutions of alkali amines such as dimethylethanolamine, alcohol amines such as triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, cyclic amines such as pyrrole and piperidine, etc. Can be used. Furthermore, alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants may be added to the aqueous solution of the above alkalis in appropriate amounts.

Of these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.

[0149]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the contents of the present invention are not limited thereto.

<Synthesis of Alkali-Soluble Resin> Synthesis Example 1 (Synthesis of Resin (B-20)) 6.45 g of 4- (hydroxy-1-methylethyl) styrene and 32.5 g of 4- (t-butoxy). Carbonyloxy) styrene is dissolved in 650 ml of THF and 0.4
After adding 4 g of benzoyl peroxide, the mixture was stirred at room temperature for 1 hour and then at 60 ° C. for 24 hours. After returning to room temperature, hexane was added to precipitate the copolymer. The obtained copolymer precipitate was reprecipitated using acetone and hexane to obtain a copolymer A-1. 7.5 g of copolymer A-1 was added to 150
Dissolve in 4 ml of dioxane, 4.2 ml of hydrazine 1
The hydrate was added and stirred under a nitrogen atmosphere for 20 hours at room temperature. The mixture was added dropwise to 200 ml of an aqueous solution containing 90 ml of 2M hydrochloric acid and 25% dioxane. The precipitate obtained is washed with water, reprecipitated using acetone and water,
Resin (B-20) was obtained.

Examples 1 to 18 and Comparative Examples 1 to 8 (1) Preparation and Coating of Resist Composition Each component shown in Table 1 was added in the following amount, and the total amount of solvent was 50.0 g.
To prepare a resist composition solution. In Table 1, the ratio when a plurality of each component is used is the weight ratio. (B) Alkali-soluble resin 4.0 g (A) Total amount of acid generator 0.20 g (D) Basic compound 0.0080 g Total amount of surfactant 0.0040 g

Each sample solution was filtered with a filter of 0.1 μm, coated on a silicon wafer using a spin coater, and dried on a vacuum adsorption type hot plate at 120 ° C. for 90 seconds to give a film thickness of 0. A resist film of 0.3 μm was obtained.

[0153]

[Table 1]

The abbreviations used in Table 1 have the following meanings.

The alkali-soluble resins for comparison are as follows. P-101: Poly- (p-hydroxystyrene) Mw 10,000 Mw / Mn = 1.4 P-102: Novolac resin m-cresol / p-cresol = 45/55 (molar ratio) Mw 6,500

The organic basic compound is as follows. N1: 1,8-diazabicyclo [4.3.0] nona-5
-Ene, N2: 2,6-diisopropylaniline, N3: 4-dimethylaminopyridine, N4: 2,4,5-triphenylimidazole, N5: triethylamine, N6: 1,5-diazabicyclo [4.3.0]. Nona-5
-Ene, N7: 1,5-diazabicyclo [2.2.2] octane, N8: hexamethylenetetramine, N9: CHMETU, N10: bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) sebacate, N11: piperazine, N12: phenylguanidine,

The surfactants are as follows. W1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine type), W2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine and silicone type), W3: Polysiloxane polymer KP -341 (produced by Shin-Etsu Chemical Co., Ltd.), W4: polyoxyethylene triphenyl ether, W5: Troisol S-366 (Troy Chemical Co., Ltd.)
Made),

The solvent is as follows. S1: propylene glycol monomethyl ether acetate, S2: propylene glycol monomethyl ether propionate, S3: ethyl lactate, S4: butyl acetate, S5: 2-heptanone, S6: propylene glycol monomethyl ether, S7: ethoxytyl propionate. , S8: γ-butyrolactone, S9: ethylene carbonate, S10: propylene carbonate, S11: cyclohexanone

(2) Preparation of resist pattern An electron beam drawing device (accelerating voltage 50 kV) was applied to this resist film.
Was used for irradiation. After irradiation, heating was performed for 60 seconds on a vacuum adsorption type hot plate at 110 ° C. for 2.3.
8% tetramethylammonium hydroxide (T
MAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds and dried. The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope, and the resist was evaluated as follows. The results of these evaluations are shown in Table 2.

[Sensitivity]: Sensitivity was defined as the minimum irradiation dose when resolving a line having a line width of 0.20 μm (line: space = 1: 1). [Resolving power]: The limiting resolving power (the line and the space are separated and resolving) at the minimum irradiation amount for resolving a line having a line width of 0.20 μm (line: space = 1: 1) was taken as the resolving power. 0.
For those in which the 20 μm line (line: space = 1: 1) did not resolve, the limit resolution was defined as the resolution.

Sensitivity fluctuation rate: The resist composition solution (coating solution) prepared as described above was evaluated for sensitivity (exposure amount before storage) immediately after preparation as described above, and the composition solution was measured at 4%. The sensitivity (exposure amount after storage) after standing for 1 week at ° C was evaluated, and the sensitivity variation rate was evaluated by the following formula. Sensitivity variation rate (%) = {(exposure amount before storage)-(exposure amount after storage)} / (exposure amount before storage) × 100

[Edge roughness]: The edge roughness was measured using a length-measuring scanning electron microscope (SEM).
13 μm line and space (line / space =
1 / 1.2) The edge roughness of the pattern is used to detect the line pattern edge at a plurality of positions within the measurement monitor, and the variance (3σ) of variations in the detected positions is used as the index of the edge roughness. The smaller this value is preferable.

[0163]

[Table 2]

The results shown in Table 2 show that the composition of the present invention shows sensitivity, resolution, sensitivity variation and line edge roughness.
It shows that it has excellent performance. Similar results were obtained with X-ray irradiation.

From these, it can be seen that the negative resist composition of the present invention is suitable for electron beam or X-ray lithography.

[0166]

EFFECTS OF THE INVENTION The present invention is intended to solve the problems of the technique for improving the original performance of microfabrication using actinic rays or radiation, and particularly, the sensitivity and resolution of the use of electron beams or X-rays. It is possible to provide a negative resist composition satisfying the characteristics of sensitivity variation and line edge roughness.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yutaka Adegawa             Fuji-Sha, 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture             Shin Film Co., Ltd. F term (reference) 2H025 AA01 AA02 AA03 AB16 AC08                       AD01 BE00 BE10 CB41 CB42                       CC03 CC20                 4J100 AB02Q AB07P AB07Q AB07R                       AJ02Q AL03Q BA02Q BA03P                       BA03Q BA03R BA16Q BC03P                       BC04P CA04 CA05 DA36                       JA38

Claims (2)

[Claims] 1. By (A) irradiation with actinic rays or radiation
A compound generating a sulfonic acid, (B) the following general formula (1)
A containing a repeating unit having a partial structure represented by
Characterized by containing Lucari soluble resin and (C) solvent
A negative resist composition. [Chemical 1] In formula (1), R represents a single bond or a divalent linking group. R
₁, R₂, R₃, R_Four, R _FiveAre each independently a substituent or a
Represents a group represented by the general formula (2). However, R₁, R₂, R
₃, R_Four, R_FiveAt least one of the following general formula (2)
Represents a group represented. [Chemical 2] In formula (2), R₆, R₇Are each independently a hydrogen atom or
Represents a rukyl group. Also R₆, R₇Are connected to form a ring
Good. R₈Is a hydrogen atom, acetyl group, t-butoxyca
Represents a carbonyl group or an alkyl group. 2. The negative resist composition according to claim 1, further comprising (D) an organic basic compound.