JP2003330191A - Negative resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemically amplifying negative resist composition excellent in the performance for isolated pattern when active rays or radiation are used. <P>SOLUTION: The negative resist composition contains (A) a compound which produces an acid by radiation of active rays or radiation, (B) a crosslinking agent which crosslinks by an acid, and (C) an alkali-soluble resin having two kinds of specified structural repeating units as the structural component. <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 refined 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 an 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 used by the exposure apparatus used in photolithography has become shorter and shorter, and now active rays such as far-ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) are considered. It has become to. Furthermore, finer pattern formation has been investigated by radiation such as electron beams and X-rays.

Electron beams or X-rays are positioned as the next-generation or next-generation pattern forming technology, and have high sensitivity,
It is desired to develop a negative resist capable of achieving a high resolution and a rectangular profile shape. Of these, electron beam lithography releases energy in the process in which an accelerated electron beam collides and scatters with atoms constituting a 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. As described above, in electron beam lithography, there is a trade-off relationship between sensitivity, resolution, and resist shape, and there has been a problem how to achieve both of them. 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, monodisperse polyvinylphenol in JP-A-8-292559, and a copolymer of vinylphenol (hydroxystyrene) and butoxycarbonylstyrene in JP-A-2000-122291, Although disclosed respectively, these alkali-soluble resins have not been able to achieve both sensitivity and resolution under irradiation with electron beams or X-rays and resist shape characteristics. Regarding the cross-linking agent, methylol melamine, resol resin, epoxidized novolac resin, urea resin, etc. have been conventionally used, but these cross-linking agents are unstable to heat and can be stored as a resist solution when stored. There was a problem with stability. Patent 3
The resist compositions proposed in 000740, JP-A-9-166870, and JP-A-2-15270 also require high sensitivity under electron beam or X-ray irradiation, high resolution, and a rectangular resist shape. The characteristics were not satisfactory.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the problem of the technique for improving the original performance of microfabrication using active rays, radiation such as electron beams or X-rays. Another object of the present invention is to provide a negative resist composition having excellent isolation performance against the use of radiation or radiation.

[0006]

The objects of the present invention have been achieved by the following. (1) (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a crosslinking agent that crosslinks with an acid, and (C) a repeating unit represented by general formula (I), and a general formula (II And a alkali-soluble resin having a repeating unit represented by the formula (1) as a constituent.

[Chemical 4] In formula (I), R ₁ represents a hydrogen atom, a halogen atom or an alkyl group, L ₁ represents a divalent linking group, R represents an electron donating group, and n represents an integer of 1 to 3. When n is 2 or more, a plurality of R may be the same or different and may be linked to each other to form a ring. However, one of the two ortho-positioned substituents with respect to the hydroxyl group on the benzene ring is a hydrogen atom, and the other is R.

[Chemical 5] In formula (II), R ₂ represents a hydrogen atom, a halogen atom or an alkyl group, L ₂ represents a divalent linking group, and M represents
In the unexposed area, the homopolymer of the general formula (II) represents a group capable of suppressing alkali solubility more than poly (4-hydroxystyrene).

(2) M in the general formula (II) is a substituted or unsubstituted benzene ring, a condensed ring, or a linear or branched alkyl group having 1 to 8 carbon atoms. The negative resist composition as described in (1).

(3) The cross-linking agent that cross-links with (B) acid is
The negative resist composition as described in (1) above, which is at least one selected from the compounds represented by formulas (2) to (4) and an alkoxymethylated melamine compound.

[Chemical 6] In formulas (2) to (4), R _5's each independently represent a hydrogen atom, an alkyl group or an acyl group. In formula (2), R _{6 to} R ₉ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxyl group. X represents a single bond, a methylene group or an oxygen atom.

(4) The cross-linking agent that cross-links with (B) acid is
It is a phenol derivative having 1 to 6 benzene rings in the molecule, has two or more hydroxymethyl groups and / or alkoxymethyl groups in the whole molecule, and bonds these groups to any benzene ring atomic group. The negative resist composition as described in (1) above, which is (5) The negative resist composition as described in any one of (1) to (4) above, which further comprises (D) a basic compound.

[0010]

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

(1) Alkali-Soluble Resin The alkali-soluble resin in the present invention is a resin which is insoluble in water and soluble in an alkaline aqueous solution (also referred to as alkali-soluble resin). The alkali dissolution rate of the alkali-soluble resin was 20 measured by 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.).
Å / second or more is preferable. Especially preferably 200Å
/ Sec or more (Å is Angstrom).

The alkali-soluble resin of the present invention is a resin having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) as constituent components.

The repeating units represented by formulas (I) and (II) will be described in detail below.

In the general formulas (I) and (II), R ₁
And R ₂ each independently represent a hydrogen atom or a methyl group. L ₁ and L ₂ each independently represent a divalent linking group. Examples of the divalent linking group include a single _{bond, -CH 2 -, - COO -} , - COOCH 2 -, - OC
_{H 2 CH 2 O -, -} OCH 2 -, and -CONH-, and the like. R represents an electron-donating group, and specific examples thereof include an alkyl group, an alkoxy group, a hydroxyl group, and a thiol group. Preferably, it is a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, or a thiol group. n represents an integer of 1 to 3. When n is 2 or more, plural Rs may be linked to each other to form a ring. Specific examples of the ring formed include:
Examples thereof include a dioxole ring, a methyl-substituted dioxole ring, an ethyl-substituted dioxole ring, a phenyl-substituted dioxole ring, a dimethyl-substituted dioxole ring and a dioxane ring. In the general formula (I), one of the two ortho-positioned substituents with respect to the hydroxyl group on the benzene ring is a hydrogen atom, and the other is R.

In the general formula (II), M is an unexposed portion and the homopolymer of the general formula (II) is poly (4-).
(Hydroxystyrene) is a group that suppresses alkali solubility, and is preferably a substituted or unsubstituted benzene ring, a condensed ring, or a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of the condensed ring include naphthalene, anthracene and pyrene. As the benzene substituent, for example, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms,
Examples thereof include an acetyl group, a halogen atom and an acid-decomposable group.

Examples of the acid-decomposable group include tert-butyl ether, tert-amyl ether, trimethylsilyl ether, tert-butyldimethylsilyl ether,
Tetrahydropyranyl ether, tetrahydrofuranyl ether, methoxyethyl ether, ethoxyethyl ether, propoxyethyl ether, butoxyethyl ether, methoxypropyl ether, ethoxypropyl ether, tert-butyl ester, tert-amyl ester, trimethylsilyl ester, tert-butyldimethylsilyl Each group such as ester, tetrahydropyranyl ester, tetrahydrofuranyl ester, methoxyethyl ester, ethoxyethyl ester, propoxyethyl ester, butoxyethyl ester, methoxypropyl ester, ethoxypropyl ester, tert-butoxycarbonyl ether, tert-amyloxycarbonyl ether But is not limited to these No. Of these, tert-
The butoxycarbonyl ether group is preferable because it has a good balance of acid decomposability and alkali dissolution inhibiting power, and when used as a resist, the pattern shape is improved.

<Measurement Method of Alkali Solubility> Mw = 8,0
00, poly (4-hydroxystyrene) of Mw / Mn = 2.00 and the homopolymer of general formula (II) were dissolved in an optimum solvent to prepare a 16 mass% solution. The sample solution was applied onto 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 polymer film having a thickness of 1.0 μm. The obtained polymer film was immersed in a 2.38% tetraammonium hydroxide (TMAH) aqueous solution, and the time until the film thickness became 0 was measured. Compare the measured time,
Those that took longer than poly (4-hydroxystyrene) were judged to have suppressed alkali solubility.

Preferred specific examples of the repeating unit represented by formula (I) are shown below, but the invention is not limited thereto.

[0019]

[Chemical 7]

[0020]

[Chemical 8]

Specific preferred examples of the repeating unit represented by the general formula (II) are shown below, but the invention is not limited thereto.

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

The alkali-soluble resin used in the present invention may contain a repeating unit other than the repeating units represented by the general formulas (I) and (II).

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

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

The alkali-soluble resin in the present invention can be synthesized by a known method such as radical polymerization, cationic polymerization and anionic polymerization. It is the simplest to carry out radical polymerization by combining the corresponding monomers, but depending on the monomer, more suitable synthesis is possible 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, the desired polymer can be obtained by polymerizing the monomer having an appropriate protective group introduced therein and deprotecting it 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. Regarding the polymerization method, Experimental Chemistry Course 28 Polymer Synthesis, New Experimental Chemistry Course 19
It is described in Polymer Chemistry [I] and the like.

The weight average molecular weight (Mw) of the alkali-soluble resin of the present invention is preferably 1,000 to 1,000,
000, more preferably 2,000 to 500,000,
Particularly preferably, it is 3,000 to 100,000.

The molecular weight distribution (Mw / Mn) of the alkali-soluble resin that can be synthesized by the above synthesis method is 1.0 to
It is preferably 2.5, 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 (C-1) to (C-15) of the alkali-soluble resin resin of the present invention are shown below, but the invention is not limited thereto. Also, the ratio of repeating units,
The weight average molecular weight and polydispersity are also shown, but the present invention is not limited to these.

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

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.

Another particularly preferred alkali-soluble resin is
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 mass 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 mass 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 mass 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 of the general formula (I) and the repeating unit of the general formula (II) of the present invention is 30 to 90 based on the total mass of the resist composition (excluding the solvent). % By mass, preferably 50 to
It is 80 mass%. 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 units of the general formula (I) and the general formula (II) as the total amount of the resist composition (solvent The amount is usually 30 to 90% by mass, preferably 50 to 80% by mass.

(B) Crosslinking Agent The compound used in the present invention which is crosslinked by an acid (hereinafter, appropriately referred to as an acid crosslinking agent or simply a crosslinking agent) is an acid,
For example, it is a compound capable of crosslinking an alkali-soluble resin in the presence of an acid generated by irradiation with radiation. Examples of such a cross-linking agent include, for example, one or more kinds of substituents having cross-linking reactivity with an alkali-soluble resin (hereinafter, referred to as "cross-linking substituents").
Say. ).

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 group-containing substituents such as glycidyl ester group and glycidylamino group; (v) Aryloxyalkyl groups such as benzyloxymethyl group and benzoyloxymethyl group, aromatic derivatives such as aralkyloxyalkyl groups; (vi) Vinyl group , Isopropenyl group, etc. It can be mentioned sex multiple bond-containing substituent group. 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, Carboxy Carboxymethyl group-containing compounds such as chill group-containing 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 resins Examples thereof include epoxy compounds such as epoxy compounds and poly (hydroxystyrene) epoxy compounds.

As the cross-linking agent, a resin in which the above-mentioned cross-linkable 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 alkoxymethylated urea compound or its resin,
Alternatively, an alkoxymethylated glycoluril compound or a resin thereof is preferable. Particularly preferable crosslinking agents (B1) include compounds represented by the above formulas (2) to (4) and alkoxymethylated melamine compounds.

R ₅ in the 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.

[0050]

[Chemical 16]

[0051]

[Chemical 17]

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, a particularly preferred cross-linking agent (B2) is a phenol derivative having 1 to 6 benzene rings in the molecule, and has 2 or more hydroxymethyl groups and / or alkoxymethyl groups in the whole molecule. 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.

[0055]

[Chemical 18]

[0056]

[Chemical 19]

[0057]

[Chemical 20]

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

[0060]

[Chemical formula 23]

(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 a phenol derivative having a hydroxymethyl group or an alkoxymethyl group may be used in combination. .

(A) Compound that Generates Acid upon Irradiation with Actinic Rays or Radiation (Acid Generator) The acid generator used in the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation. Photoinitiators for cationic polymerization, photoinitiators for radical photopolymerization, photobleaching agents for dyes, photochromic agents, or known light used for micro resists (UV of 400 to 200 nm, deep UV (g). Ray, h ray, i ray, KrF excimer laser light)), ArF excimer laser light, an electron beam, an X ray, a molecular beam or an ion beam, and a compound or mixture thereof that generates an acid. Can be used.

Other acid generators used in the present invention include, for example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and other onium salts,
Organic halogen compounds, organic metal / organic halides, o
Examples thereof include an acid generator having a nitrobenzyl type protecting group, a compound represented by iminosulfonate and the like, which photolyzes to generate a sulfonic acid, a disulfone compound, a diazoketosulfone, a diazodisulfone compound and the like.
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 acid generators, one that can be effectively used is an acid generator whose anion has a fluorine atom. For example, the cation part is composed of iodonium or sulfonium, and the anion part is R ^F SO ₃
^- (In the formula, R ^F represents a fluorine-substituted alkyl group having 1 to 10 carbon atoms), an acid generator selected from sulfonates composed of anions 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. The cation part of the acid generator is preferably one of the following general formulas (I) to (II
It is represented by I).

[0070]

[Chemical formula 24]

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 (A1-1) to (A1) of the acid generator that can be used in the present invention.
-64) is shown below.

[0075]

[Chemical 25]

[0076]

[Chemical formula 26]

[0077]

[Chemical 27]

[0078]

[Chemical 28]

[0079]

[Chemical 29]

[0080]

[Chemical 30]

[0081]

[Chemical 31]

[0082]

[Chemical 32]

Further, the following acid generators can be preferably used. (1) The following general formula (PAG) substituted with a trihalomethyl group
1) an oxazole derivative or a general formula (PAG
An S-triazine derivative represented by 2).

[0084]

[Chemical 33]

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y)
₃ is shown. Y represents a chlorine atom or a bromine atom. The following compounds can be specifically mentioned, but the compounds are not limited to these.

[0086]

[Chemical 34]

[0087]

[Chemical 35]

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

[0089]

[Chemical 36]

In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ ,
^R204 and ^R205 each independently represent a substituted or unsubstituted alkyl group or aryl group. Z ⁻ represents a counter anion, for example, BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , Si.
Condensed polynuclear aromatic sulfonate anion such as perfluoroalkane sulfonate anion such as F ₆ ²⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonate anion, naphthalene-1-sulfonate anion, anthraquinone sulfonate Examples thereof include anion dyes and sulfonic acid group-containing dyes, but are not limited thereto.

Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0092]

[Chemical 37]

[0093]

[Chemical 38]

[0094]

[Chemical Formula 39]

[0095]

[Chemical 40]

[0096]

[Chemical 41]

[0097]

[Chemical 42]

[0098]

[Chemical 43]

[0099]

[Chemical 44]

The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, and are described in, for example, US Pat.
It can be synthesized by the methods described in 2,807,648 and 4,247,473, and JP-A-53-101,331.

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

[0102]

[Chemical formula 45]

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.

[0104]

[Chemical formula 46]

[0105]

[Chemical 47]

[0106]

[Chemical 48]

[0107]

[Chemical 49]

[0108]

[Chemical 50]

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

[0110]

[Chemical 51]

Here, R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0112]

[Chemical 52]

The amount of these acid generators 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. It is used in the range of 0.1 to 5% by weight. If the addition amount of the acid generator is less than 0.001% by weight, the sensitivity is lowered, and if the addition amount is more than 40% by weight, the profile is deteriorated and the process (particularly baking) margin is narrowed, which is not preferable.

Other compounds that generate an acid upon irradiation with actinic rays or radiation include cationic polymerization photoinitiators, photoradical polymerization photoinitiators, photobleaching agents for dyes, photochromic agents, or micro resists. A known compound which generates an acid by light and a mixture thereof which are used in the above can be appropriately selected and used.

For example, SI Schlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) the diazonium salts described in U.S. Pat. No. 4,069,055
No. 4,069,056, Re 27,992, JP-A-3-140140
Ammonium salt, DC Necker et al, Macrom
olecules, 17,2468 (1984), CSWen et al, Teh, Proc.Conf
Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent No.
Phosphonium salts described in 4,069,055, 4,069,056, etc., JVCrivello et al, Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No.
104,143, 339,049, 410,201, JP
2-150,848, iodonium salts described in JP-A-2-296,514, JVCrivello et al, Polymer J. 17,73 (1985),
JVCrivello et al. J. Org. Chem., 43, 3055 (1978), WR
Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22,1789
(1984), JVCrivello et al, Polymer Bull., 14,279 (19
85), JVCrivello et al, Macromorecules, 14 (5), 1141 (1
981), JVCrivello et al, J.PolymerSci., Polymer Che
m.Ed., 17,2877 (1979), European Patent No. 370,693, and 161,8.
No. 11, No. 410,201, No. 339,049, No. 233,567,
No. 297,443, No. 297,442, U.S. Pat.No. 3,902,114
No. 4,933,377, 4,760,013, 4,734,444
No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,60
4,580, 3,604,581 etc. sulfonium salts,
JVCrivello et al, Macromorecules, 10 (6), 1307 (1977)
, JVCrivello et al, J. PolymerSci., Polymer Chem.E
d., 17,1047 (1979) and other selenonium salts, CSWe
n etal, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oc
Onium salts such as arsonium salts described in t (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605, JP-A-48-
36281, JP 55-32070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-582.
41, JP 62-212401, JP 63-70243, JP
63-298339 and other organic halogen compounds, K. Meier
et al, J. Rad. Curing, 13 (4), 26 (1986), TPGilletal, Ino
rg.Chem., 19,3007 (1980), D.Astruc, Acc.Chem.Res., 19
(12), 377 (1896), organic metal / organic halides described in JP-A-2-61445, S. Hayase et al., J. Polymer Sci.,
25,753 (1987), E. Reichmanis et al, J. Pholymer Sci., Po
lymer Chem. Ed., 23, 1 (1985), QQZhu et al., J. Photoche
m., 36,85,39,317 (1987), B.Amitetal, Tetrahedron Let
t., (24) 2205 (1973), DHR Barton et al., J. Chem Soc., 35.
71 (1965), PMCollins et al, J. Chem. SoC., Perkin I, 16
95 (1975), M. Rudinstein et al, Tetrahedron Lett., (1
7), 1445 (1975), JWWalker et al J. Am. Chem. Soc., 110, 7
170 (1988), SCBusman et al., J. Imaging Technol., 11
(4), 191 (1985), HMHoulihan et al, Macormolecules, 2
1, 2001 (1988), PMCollins et al, J. Chem. Soc., Chem.Com
mun., 532 (1972), S.Hayase et al, Macromolecules, 18,179
9 (1985), E. Reichmanis et al, J. Electrochem. Soc., Soli
d State Sci.Technol., 130 (6), FMHoulihan etal, Mac
romolcules, 21, 2001 (1988), European Patent No. 0290,750, 0
46,083, 156,535, 271,851, 0,388,343
M.TUNOOKA, a photo-acid generator having an o-nitrobenzyl type protecting group described in U.S. Pat. Nos. 3,901,710, 4,181,531, JP-A-60-198538 and JP-A-53-133022.
et al, Polymer Preprints Japan, 35 (8), G. Berner et al,
J.Rad.Curing, 13 (4), WJMijs etal, Coating Techno
l., 55 (697), 45 (1983), Akzo, H.Adachi etal, Polymer P
reprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515
No., No. 044,115, No. 618,564, No. 0101,122,
U.S. Pat.Nos. 4,371,605 and 4,431,774, Japanese Patent Laid-Open No. 64-1
No. 8143, JP-A-2-245756, JP-A-3-140109 and the like compounds such as iminosulfonates which photolyze to generate sulfonic acid, JP-A-61-166544 and the like A disulfone compound can be mentioned.

Further, a group generating an acid by these light,
Alternatively, a compound in which a compound is introduced into the main chain or side chain of a polymer, for example, ME Woodhouse et al., J. Am. Chem. So.
c., 104,5586 (1982), SPPappas et al, J. Imaging Sc
i., 30 (5), 218 (1986), S.Kondoetal, Makromol.Chem., Ra
pid Commun., 9,625 (1988), Y.Yamada et al, Makromol.C
hem., 152,153,163 (1972), JVCrivello et al, J.Polym
erSci., Polymer Chem. Ed., 17,3845 (1979), U.S. Pat.No. 3,849,137, United States Patent No. 3914407, JP-A-63-266.
53, JP 55-164824, JP 62-69263, JP
63-146038, JP-A-63-163452, JP-A-62-153853
The compounds described in JP-A-63-146029 and the like can be used.

Furthermore, VNR Villai, Synthesis, (1), 1 (198
0), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971),
DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent 126,712 and the like which generate an acid by light can also be used.

(4) Other components used in the composition of the present invention The negative resist composition of the present invention may further contain an organic basic compound, a dye, a surfactant and the like, if necessary. it can.

(4) -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.

(4) -2 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.

[0121]

[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 nitrogen-containing basic compounds may be used alone or in combination of two or more. The ratio of the compound that generates an acid upon irradiation with actinic rays or radiation and the organic basic compound in the composition is (compound that generates an acid upon irradiation with actinic rays or radiation) / (organic basic compound) (molar ratio ) = 2.5-30
It is preferably 0. If the molar ratio is less than 2.5, the sensitivity may be low and the resolution may be lowered.
If it exceeds, the resist pattern may become thicker with the passage of time from the irradiation to the heat treatment, and the resolution may decrease.
The (compound which generates an acid upon irradiation with actinic rays or radiation) / (organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

(4) -3 Solvents The negative resist composition of the present invention is dissolved in a solvent capable of dissolving 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-dimethyl Formamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used as simple substances. Or mixed to use. 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.

(4) -4 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. As the surfactant that can be used in addition to the above, specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. , Polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether and other polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan Sorbitan fatty acid esters such as monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Etc. can be mentioned.
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, 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, then irradiating with an electron beam or X-ray drawing device, and heating, developing, rinsing and drying.

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.

[0133]

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. (1) Synthesis of alkali-soluble resin (1-1) 3-methoxy-4-hydroxystyrene 1
5.0 g (0.1 mol), styrene 23.9 g (0.
23 mol) is dissolved in dry THF and 70 ° C. under a nitrogen stream.
And heated to Wako Pure Chemical Industries, Ltd. azo radical initiator V-601
2% of the total number of moles of the monomer was added. After reacting for 8 hours, the reaction solution was diluted with THF, precipitated in hexane, and purified to take out a polymer. It was decomposed with an acid according to a conventional method to obtain (C-1). The weight average molecular weight (Mw) and the molecular weight dispersity (Mw / Mn) were determined by GPC measurement. (1-2) Using the same method as above and using a protected monomer (eg, 4-benzyloxystyrene), BF ₃ ·.
Cationic polymerization with EtO ₂ is used properly (C-4)
~ (C-15) were synthesized. (1-3) 3-methoxy-4-hydroxystyrene 1
5.0 g (0.1 mol) and 4-t-butoxystyrene 10.7 g (0.067 mol) were dissolved in dry THF and the glass seal was broken using 1 mmol of s-butyllithium in a sealed tube at -78 ° C. To start the reaction. The powder was collected by precipitation in a large amount of hexane and purified. Treatment with an acid according to a standard method gave (C-3).

(2) Synthesis of cross-linking agent (2-1) Synthesis of cross-linking agent [HM-0] p-Aminophenol (1 mol) and sodium acetate (1 mol) were put in a flask together with acetone (1 liter) to prepare isobutyric acid. Chloride (1 mol) is added dropwise under ice cooling. After 5 hours, the mixture was poured into ice water to precipitate crystals, and the crystals were collected by filtration to obtain HM-0-X with a yield of 80%. This HM
-0-X (0.8 mol) and KOH (0.8 mol),
Water 500m1, 37% formalin aqueous solution (4.8mo
l) was placed in a flask, heated at 50 ° C. for 5 hours, neutralized with acetic acid, the solvent was concentrated under reduced pressure, and the obtained oily product was diluted with ethyl acetate /
It was dissolved in methanol = 1/1 and separated by SiO ₂ column chromatography, and the target product HM-0 (L ₁ = L ₂ = C
(H ₂ OH) was obtained as colorless crystals in a total yield of 50%.

[0135]

[Chemical 54]

(2-2) Synthesis of cross-linking agent [HM-1] 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl ] Benzene 20 g (Honshu Chemical Industry Co., Ltd. T
(risp-PA) was added to a 10% aqueous potassium hydroxide solution, and the mixture was stirred and dissolved. Then, while stirring this solution, 3
60 ml of 7% formalin aqueous solution 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 thoroughly with water, and then recrystallized from 30 ml of methanol to obtain 20 g of a white powder of a phenol derivative [HM-1] having a hydroxymethyl group having the following structure. The purity was 92% (liquid chromatography method).

(2-3) 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. did. Next, 1 ml of concentrated sulfuric acid was added to this solution, and the mixture was heated under reflux for 12 hours. After completion of the reaction, the reaction solution was cooled and 2 g of potassium carbonate was added. After sufficiently concentrating the 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 [MM-1] having a methoxymethyl group having the following structure. 90 purity
% (Liquid chromatography method).

[0138]

[Chemical 55]

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

[0140]

[Chemical 56]

(1) Preparation of resist and coating Each component shown in Table 1 was added in the following amounts, and the total amount of solvent was 18.0 g.
To prepare a resist composition solution. In Table 1, the ratio when a plurality of each component is used is the weight ratio. Alkali-soluble resin (C) 2.0 g Total amount of acid generator (A) 0.20 g Total amount of crosslinking agent (B) 0.35 g Basic compound (D) 0.0080 g Total amount of surfactant 0.0040 g Each sample solution After being filtered with a 0.1 μm filter,
A silicon wafer was coated using a spin coater and dried at 120 ° C. for 90 seconds on a vacuum adsorption type hot plate to obtain a resist film having a thickness of 0.3 μm.

[0142]

[Table 1]

The abbreviations used in Table 1 have the following meanings.

<Comparative Alkali-Soluble Resin> P-100
~ 104:

[0145]

[Chemical 57]

The nitrogen-containing basic compound is as follows. (1) 1,8-diazabicyclo [4.3.0] nona-5
-Ene, (2) 2,6-diisopropylaniline,
(3) 4-dimethylaminopyridine, (4) 2,4,5
-Triphenylimidazole, (5) triethylamine, (6) 1,5-diazabicyclo [4.3.0] non-5-ene, (7) 1,5-diazabicyclo [2.2.
2] octane, (8) hexamethylenetetramine,
(9) CHMETU, (10) bis (1, 2, 2, 6,
6-pentamethyl-4-piperidyl) sebacate, (1
1) piperazine, (12) 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 Ke) was formed on this resist film.
V) was used for irradiation. 110 ° C after irradiation
Heating for 60 seconds on the vacuum adsorption hot plate of
It was immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds and dried. The obtained pattern was observed with a scanning electron microscope. Evaluation was carried out by the following methods, and the results are shown in Table 2.

[Isolation performance]: The minimum irradiation energy when resolving a 0.15 μm line (line: space = 1: 1) was taken as the sensitivity, and determined by the above dense line pattern (line: space = 1: 1). With regard to sensitivity, the resolution limit of resolution of an isolated line pattern (line: space = 1: 10) was defined as the isolation performance.

[0151]

[Table 2]

The results in Table 2 show that the composition of the present invention has excellent isolation performance. Similar results were obtained with X-ray irradiation.

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

[0154]

Industrial Applicability According to the present invention, a negative photosensitive composition for electron beam or X-ray having excellent sensitivity and resolution and having a rectangular profile can be provided.

Continued front page    F-term (reference) 2H025 AA02 AA03 AB16 AC05 AC06                       AD01 BE00 CB14 CB16 CB17                       CB41 CB45 CC17 CC20 FA17

Claims (5)

[Claims] 1. A compound which generates an acid upon irradiation with actinic rays or radiation, (B) a crosslinking agent which crosslinks with an acid, and (C) a repeating unit represented by the general formula (I); A negative resist composition containing an alkali-soluble resin having a repeating unit represented by (II) as a constituent. [Chemical 1] In formula (I), R ₁ represents a hydrogen atom, a halogen atom or an alkyl group, L ₁ represents a divalent linking group, R represents an electron donating group, and n represents an integer of 1 to 3. When n is 2 or more, a plurality of R may be the same or different and may be linked to each other to form a ring. However, one of the two ortho-positioned substituents with respect to the hydroxyl group on the benzene ring is a hydrogen atom, and the other is R. [Chemical 2] In formula (II), R ₂ represents a hydrogen atom, a halogen atom or an alkyl group, L ₂ represents a divalent linking group, and M represents
In the unexposed area, the homopolymer of the general formula (II) represents a group capable of suppressing alkali solubility more than poly (4-hydroxystyrene). 2. M in the general formula (II) is a substituted or unsubstituted benzene ring, a condensed ring, or a linear or branched alkyl group having 1 to 8 carbon atoms. 2. The negative resist composition as described in 1. 3. The (B) acid-crosslinking agent is at least one selected from the compounds represented by the general formulas (2) to (4) and an alkoxymethylated melamine compound. The negative resist composition according to claim 1. [Chemical 3] In formulas (2) to (4), R _5's each independently represent a hydrogen atom, an alkyl group or an acyl group. In formula (2), R _{6 to} R ₉ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxyl group. X represents a single bond, a methylene group or an oxygen atom. 4. The (B) acid-crosslinking agent is a phenol derivative having 1 to 6 benzene rings in the molecule, and has 2 or more hydroxymethyl groups and / or alkoxymethyl groups in the entire molecule. The negative resist composition according to claim 1, which is a compound in which these groups are bonded to any benzene ring atomic group. 5. The negative resist composition according to any one of claims 1 to 4, further comprising (D) a basic compound.