KR20140041649A - Laminate comprising negative resist composition and pattern forming method using the same - Google Patents

Abstract

(A) an alkali-soluble polymer comprising specific recurring units defined in particular; (B) a crosslinking agent capable of crosslinking with the alkali-soluble polymer (A) under the action of an acid; (C) a compound capable of generating an acid upon irradiation with an actinic ray or radiation; (D) certain quaternary ammonium salts, as defined in particular; And (E) an organic carboxylic acid, and a method of forming a pattern using the composition.

Description

TECHNICAL FIELD The present invention relates to a laminate including a negative resist composition and a pattern forming method using the laminate.

The present invention relates to a negative resist composition suitably used for ultra-microlithography, such as the manufacture of VLSI or high-capacity microchips or other manufacturing processes, and a pattern forming method using the same. In particular, the present invention relates to a negative resist composition capable of forming a high-resolution pattern using electron beams or X-rays and a pattern forming method using the same. That is, the present invention relates to a negative resist composition for use in a process using a substrate having a specific underlying line thereon.

Conventionally, fine processing by lithography using a photoresist composition has been performed in the manufacture of semiconductor devices such as IC and LSI. In recent years, it is required to form ultrafine patterns in submicron or quarter micron regions with the integration of integrated circuits. In response to this demand, the exposure wavelength also tends to become gradually shorter, for example, from the g line to the i line or further to the KrF excimer laser beam. At present, lithography using an electron beam or X-ray in addition to excimer laser light is under development.

In particular, electron beam lithography is positioned as a next-generation or next-generation pattern forming technology, and a negative type resist of high sensitivity and high resolution is required.

In addition, the electron beam lithography is widely used in the manufacture of photomasks used in semiconductor exposures because of its high resolution characteristics. The photomask manufacturing process is as follows. A shielding layer composed mainly of a shielding material such as chromium is formed on a transparent substrate such as a glass substrate to form a shielding substrate, a resist layer is formed thereon, and a resist pattern is formed on the shielding layer by selectively exposing the shielding layer. Subsequently, a photomask including a transparent substrate having a shielding layer having a predetermined pattern thereon is obtained by etching a shielding layer of a portion where no pattern is formed and transferring the pattern to the shielding layer using the resist pattern as a mask .

In a process using an electron beam which is different from the batch exposure of light, high sensitivity is very important in order to shorten the processing time. In the case of a negative type resist for electron beam, however, And the edge roughness is deteriorated. Thus, development of a resist which can satisfy both of these characteristics is strongly demanded. Here, the line edge roughness means that the edge of the resist at the interface between the pattern and the substrate irregularly fluctuates in the direction perpendicular to the line direction due to the characteristics of the resist, and the edge appears uneven when viewed from directly above the pattern. Such unevenness is transferred by the etching step using the resist as a mask, and the dimensional accuracy is lowered. In particular, line edge roughness is a very important problem to be solved in an ultrafine region of 0.25 탆 or less.

In addition, deterioration of the pattern profile occurs when a resist pattern is formed on a shielding layer used in manufacturing a photomask. Particularly, when a negative type resist is used, collapse of the pattern due to corrosion of the interface with the substrate occurs, which causes deterioration of resolving power, which is a problem.

High sensitivity and high resolution, good pattern profile and good line edge roughness are very important in terms of how to satisfy all these characteristics simultaneously in a trade-off.

A chemically amplified resist mainly using an acid catalyst reaction is used for the electron beam or X-ray lithography process from the viewpoint of high sensitivity. In the case of the negative type resist, an alkali soluble resin, a crosslinking agent, an acid generator and an additive A chemically amplified resist composition is effectively used.

Various studies have been carried out to improve the performance of the chemically amplified negative resist. The following investigations have been made with additives, especially ammonium salt type additives. For example, JP-A-4-51243 discloses a combination of a tetraalkylammonium salt and a novolak resin, JP-A-8-110638 discloses a trialkylammonium hydroxide, JP-A-11-149159 Discloses the bonding of a tetraalkylammonium salt with a polymer having a carboxylic acid in its side chain.

However, it is impossible to satisfy both of high sensitivity in the ultrafine region, high resolution, good pattern profile, good line edge roughness and good vacuum PED characteristics at the same time by any combination of these conventionally known compounds.

Further, in JP-A 10-186660, the use of an organic carboxylic acid has been studied, but the use of a specific resin and a specific ammonium salt is not disclosed. Japanese Patent Application Laid-Open No. 2003-295439 discloses an example using an ammonium salt, but an example using an organic carboxylic acid can not be found. Further, none of these patent publications disclose improvement of line edge roughness while showing a good pattern profile with reduction of corrosion, which is an effect of the present invention.

SUMMARY OF THE INVENTION An object of the present invention is to solve the technical problem of improving the performance in the microfabrication process of a semiconductor device or a photomask, and in particular, to provide a semiconductor device or a photomask using an electron beam or X-ray with high sensitivity, high resolution, Line edge roughness, and satisfactory PED characteristics in vacuum at the same time, and a pattern forming method using the composition.

As a result of intensive studies, the inventors of the present invention have found that the object of the present invention can be achieved by a negative resist composition having a specific structure of an alkali-soluble resin, a crosslinking agent, an acid generator, and an ammonium salt of a specific structure and an organic carboxylic acid.

That is, the present invention is as follows.

(1) A layered product in which a vapor-deposited film is formed on a surface of a substrate and a layer containing a negative resist composition is formed on the vapor-deposited film,

Wherein the vapor-deposited film is formed of Cr, Mo, MoSi, TaSi, an oxide thereof, or a nitride thereof,

The negative resist composition

(A) an alkali-soluble polymer containing a repeating unit represented by the general formula (1);

(B) a crosslinking agent capable of crosslinking with the alkali-soluble polymer (A) under the action of an acid;

(C) a compound capable of generating an acid upon irradiation with an actinic ray or radiation;

(D) a quaternary ammonium salt represented by the following general formula (2); And

(E) an organic carboxylic acid,

Wherein the mass ratio of the quaternary ammonium salt (D) to the organic carboxylic acid (E) is 10-90: 90-10.

General formula (1):

R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group or an alkylcarbamoyl group, And n represents an integer of 1 to 3.)

General formula (2):

(R ₃ ~ R ₆ are each independently an alkyl group, an alkenyl group, an aryl group or an aralkyl group; B ^- is OH ^- group, a halogen atom, R ₇ -CO ₂ ^- group or an R ₇ -SO ₃ ^- group; And R < ₇ > represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.

(2) In the above (1)

Wherein the crosslinking agent (B) is a phenol compound containing two or more benzene rings in the molecule and not containing a nitrogen atom.

(3) forming the laminate according to (1) or (2) above; And a step of exposing and developing the layer containing the negative resist composition.

Further, preferred embodiments of the present invention are as follows.

(4) In the above (1) or (2)

The alkali-soluble polymer (A) further contains at least one repeating unit selected from the repeating units represented by the general formulas (3), (4) and (5)

The general formula (3)

In general formula (4):

The general formula (5)

는 하기 구조로부터 선택된 임의의 기를 나타낸다.)(

Represents any group selected from the following structures.

(Wherein A has the same meaning as A in the formula (1), X represents a single bond, -COO- group, -O- group or -CON (R ₁₆ ) - group, R ₁₆ represents a hydrogen atom or an alkyl group R ₁₁ to R ₁₅ each independently represent the same meaning as R _{1 in} Formula (1); R ₁₀₁ to R ₁₀₆ each independently represent a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkyl An alkenyl group, an aryl group, an aralkyl group or a carboxy group; a to f each independently represent an integer of 0 to 3.)

(5) In any one of the above-mentioned (1), (2) and (4)

The crosslinking agent (B) is a phenol derivative having a molecular weight of 1,200 or less, 3 to 5 benzene rings in the molecule, and 2 or more hydroxymethyl groups or alkoxymethyl groups, wherein the two or more hydroxymethyl groups or alkoxymethyl groups Is bonded intensively to at least one of the benzene rings or is dispersed and bound to the benzene ring.

(6) In any one of (1), (2), (4) and (5)

Wherein the organic carboxylic acid (E) is at least one selected from the group consisting of saturated or unsaturated aliphatic carboxylic acids, alicyclic carboxylic acids, oxycarboxylic acids, alkoxycarboxylic acids, ketocarboxylic acids and aromatic carboxylic acids.

(7) As for (6),

Wherein the organic carboxylic acid (E) is at least one selected from the group consisting of benzoic acid, 1-hydroxy-2-naphthoic acid, and 2-hydroxy-3-naphthoic acid.

(8) In the above (1)

Wherein the quaternary ammonium salt (D) is contained in an amount of 0.05 to 3% by mass based on the total solid content of the negative resist composition and the organic carboxylic acid (E) is contained in an amount of 0.01 to 3% by mass based on the total solid content of the negative resist composition The laminate

According to the present invention, it is possible to provide a negative resist composition excellent in sensitivity, resolution, pattern profile, line edge roughness and PED property in vacuum, and a pattern forming method using the composition.

The negative resist composition of the present invention will be described in detail below.

Incidentally, unless specifically stated that the group (atomic group) is substituted or unsubstituted, the group includes both groups having no substituent group and groups having a substituent group. For example, the "alkyl group" includes an alkyl group (substituted alkyl group) having a substituent as well as an alkyl group (unsubstituted alkyl group) having no substituent.

[1] (a) An alkali-soluble polymer

The alkali-soluble polymer used in the present invention contains the repeating unit represented by the general formula (1) as an essential component.

In the general formula (1), the alkyl group represented by A is preferably an alkyl group having 1 to 3 carbon atoms. Examples of halogen atoms which are A include Cl, Br and F. [

A is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group or an ethyl group), more preferably a hydrogen atom or a methyl group.

Examples of halogen atoms of R < ₁ > and R < ₂ > include Cl, Br, F and I.

The alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, alkylcarbonyloxy group or alkylsulfonyloxy group represented by R ₁ and R ₂ may have a substituent. Also, R ₁ and R ₂ may combine to form a ring.

R ₁ and R ₂ The A linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent independently, an alkenyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, An aralkyl group having 7 to 16 carbon atoms which may have a substituent, an alkoxy group having 1 to 8 carbon atoms which may have a substituent or an alkylcarbonyloxy group having 1 to 8 carbon atoms which may have a substituent .

Examples of the substituent include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group and a hexyl group), an aryl group (e.g. a phenyl group and a naphthyl group), an aralkyl group, , An alkoxy group (e.g., methoxy group, ethoxy group, butoxy group, octyloxy group, dodecyloxy group), an acyl group (for example, acetyl group, propanoyl group or benzoyl group) and an oxo group.

R ₁ and R ₂ are Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, or an alkylcarbonyloxy group having 1 to 4 carbon atoms which may have a substituent An alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, propyl group or isopropyl group) or an alkoxy group having 1 to 3 carbon atoms (e.g., a methyl group, an ethyl group, More preferably a methoxy group, an ethoxy group, a propyloxy group, or an isopropyloxy group).

The polymer of the component (A) used in the present invention may contain at least one repeating unit represented by any of the general formulas (3) to (5) together with the repeating unit represented by the general formula (1).

In the general formulas (3) to (5), A has the same meaning as A in the general formula (1), X is a single bond, -COO- group, -O- group or -CON (R ₁₆ ) And R ₁₆ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group, an ethyl group or a propyl group). X is preferably a single bond, -COO- group, or -CON (R ₁₆ ) group, more preferably -COO- group.

R ₁₁ to R ₁₅ silver Each independently have the same meaning as R ₁ in the general formula (1).

R ₁₀₁ to R ₁₀₆ each independently represents a hydroxyl group, a halogen atom (Cl, Br, F or I), a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, a linear or branched A linear or branched alkylcarbonyloxy group having 1 to 8 carbon atoms which may have a substituent, a straight-chain or branched alkylsulfonyloxy group having 1 to 8 carbon atoms which may have a substituent, a carbon number which may have a substituent An alkenyl group having 1 to 8 carbon atoms, an aryl group having 7 to 15 carbon atoms which may have a substituent, an aralkyl group having 7 to 16 carbon atoms which may have a substituent, or a carboxy group.

Examples of these substituents are the same as the examples of the substituent of R ₁ in the general formula (1).

R ₁₀₁ to R ₁₀₆ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, An alkyl group having 1 to 3 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group or an isopropyl group), an alkoxy group having 1 to 3 carbon atoms (For example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group), or an alkylcarbonyloxy group having 1 to 3 carbon atoms (e.g., an acetyl group or a propionyl group).

a to f each independently represent an integer of 0 to 3;

The polymer of the component (A) used in the present invention is a resin having only one repeating unit represented by the general formula (1), a resin having two or more repeating units represented by the general formula (1) ) And a resin having at least one repeating unit selected from the repeating units represented by the general formulas (3) to (5), and the resin having a repeating unit represented by the general formula Other polymerizable monomers may be polymerized therein.

Examples of such polymerizable monomers include styrene, alkyl substituted styrene, alkoxy substituted styrene, O-alkyl styrene, O-acylated styrene, hydrogenated hydroxystyrene, maleic anhydride, acrylic acid derivatives (e.g., But are not limited to, methacrylic acid derivatives (e.g., methacrylic acid, methacrylic acid esters), N-substituted maleimide, acrylonitrile, and methacrylonitrile

In the polymer of the component (A) used in the present invention, the content of the repeating unit represented by the general formula (1) is generally 50 to 100 mol%, preferably 70 to 100%.

In the polymer of the component (A), the ratio between the repeating unit represented by the general formula (1) and the repeating unit (s) represented by the general formulas (3) to (5) 50, more preferably 100/0 to 60/40, and even more preferably 100/0 to 70/30.

The weight average molecular weight of the polymer of the component (A) is preferably 1,000 to 200,000, more preferably 2,000 to 50,000.

The molecular weight distribution (Mw / Mn) of the polymer of the component (A) is preferably 1.0 to 2.0, more preferably 1.0 to 1.35.

The addition amount of the polymer of the component (A) is preferably 30 to 95 mass%, more preferably 40 to 90 mass%, and even more preferably 50 to 80 mass% with respect to the total solid content of the composition. Equivalent to the weight ratio.)

Here, the molecular weight and the molecular weight distribution of the polymer are defined as polystyrene conversion values by GPC measurement.

The polymer of the component (A) can be synthesized by a known radical polymerization method or an anionic polymerization method. For example, in the radical polymerization method, a vinyl monomer is dissolved in a suitable organic solvent, and a peroxide (for example, benzoyl peroxide), a nitrile compound (for example, azobisisobutyronitrile) or an oxidation- For example, cumene hydroperoxide-ferrous salt) as an initiator and reacting at room temperature or under heating to obtain a polymer. In the anionic polymerization method, the polymer can be obtained by dissolving the vinyl monomer in an appropriate organic solvent, and reacting it with a metal compound (for example, butyllithium) as an initiator, usually under cooling.

 Specific examples of the alkali-soluble polymer of component (A) used in the present invention are shown below, but the present invention is not limited thereto.

In the above embodiments, n represents a positive number, and x, y, and z represent the molar ratio of the composition. In the case of a resin containing two components, the molar ratio is preferably in the range of x = 10 to 95 and y = 5 to 90, x = 40 to 90 and y = 10 to 60, = 10 to 90, y = 5 to 85 and 5 to 85, x = 40 to 80, y = 10 to 50, and z = 10 to 50.

These polymers may be used alone or in combination of two or more.

[2] Acid crosslinking agent (component (B))

In the present invention, a compound capable of crosslinking under the action of an acid (hereinafter also referred to as "acid crosslinking agent" or simply "crosslinking agent") is used together with the above alkali-soluble polymer. A known acid cross-linking agent can be effectively used herein.

The acid crosslinking agent is preferably a compound or resin having two or more hydroxymethyl groups, alkoxymethyl groups, acyloxymethyl groups or alkoxymethyl ether groups, or an epoxy compound.

More preferred examples thereof include an alkoxymethylated or acyloxymethylated melanin compound or resin, an alkoxymethylated or acyloxymethylated urea compound or resin, a hydroxymethylated or alkoxymethylated phenol compound or resin, and an alkoxymethyl-ethylated phenol compound or resin Lt; / RTI >

 The component (B) has a molecular weight of 1,200 or less, contains 3 to 5 benzene rings in the molecule, and has 2 or more hydroxymethyl groups or alkoxymethyl groups, and the hydroxymethyl group or alkoxymethyl group has at least one benzene ring Or a phenol derivative bonded to the benzene ring by being dispersed in the benzene ring.

The alkoxymethyl group bonded to the benzene ring may be an alkoxymethyl group having 6 or less carbon atoms, specifically, a methoxymethyl group, an ethoxymethyl group, a n-propoxymethyl group, an i-propoxymethyl group, A butoxymethyl group, or a t-butoxymethyl group. Alkoxy substituted alkoxy groups such as 2-methoxyethoxy and 2-methoxy-1-propyl are preferred.

The crosslinking agent (B) is preferably a phenol compound having two or more benzene rings in the molecule and containing no nitrogen atom.

Particularly preferred compounds among these phenol derivatives are listed below.

(Wherein L ¹ to L ⁸ May be the same or different and each represent a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group.

A phenol derivative having a hydroxymethyl group is a phenol compound having no corresponding hydroxymethyl group under a base catalyst (L ¹ to L ⁸ Each of which is a hydrogen atom) with formaldehyde. In order to prevent resinification or gelation, it is preferable to carry out the reaction at a temperature of 60 DEG C or lower. Specifically, these phenol derivatives can be synthesized by the methods described in, for example, JP-A-6-282067 and JP-A-7-64285.

A phenol derivative having an alkoxymethyl group can be obtained by reacting an alcohol with a phenol derivative having a corresponding hydroxymethyl group under an acid catalyst. In this case, it is preferable to carry out the reaction at a reaction temperature of 100 DEG C or lower in order to prevent resinification or gelation. Specifically, these phenol derivatives can be synthesized, for example, by the method described in European Patent Publication No. 632003.

A phenol derivative having a hydroxymethyl group or an alkoxymethyl group thus synthesized is preferable from the standpoint of stability upon storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the standpoint of stability upon storage.

Any of these phenol derivatives having two or more hydroxymethyl groups or alkoxymethyl groups bonded to at least one benzene ring in a concentrated manner or dispersed in a benzene ring may be used singly or in combination of two or more May be used.

Examples of preferred crosslinking agents include (i) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group described later, and (ii) an epoxy group.

Examples of the compound having (i) an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group include oligomer-melamine, which is a monomer disclosed in European Patent Publication No. 0133216 and West German Patent No. 3,634,671 and European Patent No. 3,711,264 -Formaldehyde condensates and urea-formaldehyde condensates, alkoxy substituted compounds disclosed in EP-A-0212482, and benzoguanamine-formaldehyde condensates.

More preferred examples include melamine-formaldehyde derivatives having two or more free N-hydroxymethyl groups, N-alkoxymethyl groups or N-acyloxymethyl groups, and more preferred are N-alkoxymethyl derivatives.

Examples of the epoxy compound (ii) include monomer-, dimer-, oligomer- or polymer-type epoxy compounds including at least one epoxy group. Examples of these include reaction products of bisphenol A and epichlorohydrin and reaction products of low molecular weight phenol-formaldehyde resins and epichlorohydrin. Other examples include epoxy resins described and used in U.S. Patent No. 4,026,705 and British Patent No. 1,539,192.

The crosslinking agent is preferably added in an amount of 3 to 65 mass%, more preferably 5 to 50 mass%. When the addition amount of the crosslinking agent is 3 to 65% by mass, it is possible to prevent the residual film ratio and the resolving power from being lowered, and at the same time, the stability at the time of preservation of the resist solution can be satisfactorily maintained.

In the present invention, the crosslinking agent may be used alone or in combination of two or more kinds.

For example, when other crosslinking agents such as (i) and (ii) are used in addition to the phenol derivative, the ratio between the phenol derivative and the other crosslinking agent is 100/0 to 20/80 in terms of molar ratio, 40/60, and more preferably 80/20 to 50/50.

[3] A compound capable of generating an acid upon irradiation with an actinic ray or radiation (component (C))

The negative resist composition of the present invention contains a compound capable of generating an acid upon irradiation with an actinic ray or radiation (hereinafter referred to as "acid generator").

The acid generator is a known compound which generates an acid upon irradiation with an actinic ray or radiation used for a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photoinitiator for a dye, a photochromic agent, a micro-resist, May be appropriately selected and used.

Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oxime sulfonates, diazodisulfone, disulfone and o-nitrobenzylsulfonate.

Further, compounds obtained by introducing groups or compounds capable of generating an acid upon irradiation with an actinic ray or radiation into the main chain or side chain of the polymer, such as those disclosed in U.S. Patent No. 3,849,137, German Patent No. 3,914,407, 63-26653, 55-164824, 62-69263, 63-146038, 63-163452, 62-153853 and JP-A-62-153853, The compound described in JP-A-63-146029 may be used.

Further, compounds capable of generating an acid by the light described in U.S. Patent No. 3,779,778 and European Patent No. 126,712 may be used.

Among the compounds capable of being decomposed by irradiation with an actinic ray or radiation to generate an acid, the compounds represented by the following general formulas (ZI), (ZII) and (ZIII) are preferred.

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are Each independently represent an organic group.

X ^- represents a non-nucleophilic anion, and preferred examples thereof include a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ^- , PF ₆ ^- And SbF ₆ ^- are listed. The anion is preferably an organic group containing a carbon atom.

 Preferred organic groups include organic anions represented by the following general formulas (AN1) to (AN4).

In the general formulas (AN1) and (AN2), Rc ₁ represents an organic group.

Examples of the organic group in Rc ₁ include organic groups having 1 to 30 carbon atoms, which may be substituted, alkyl or aryl groups, or some of these groups are single bonds or -O-, -CO ₂ -, -S-, _{_} -SO ₃ group, and -SO ₂ N (Rd ₁₎ - group is attached to the group are listed, such as a linking group.

Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure together with an alkyl group or an aryl group to which Rd ₁ is bonded.

More preferably, the organic group of Rc ₁ is an alkyl group whose 1-position is substituted by a fluorine atom or a fluoroalkyl group, or a phenyl group substituted by a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. When the Rc ₁ having five or more carbon atom, the carbon atom one or more it is desirable to make not replaced all of the hydrogen atoms with fluorine atoms remaining hydrogen atoms, more preferably so that the number of the hydrogen atom more than the number of fluorine atoms. The ecotoxicity can be alleviated by the absence of perfluoroalkyl groups having 5 or more carbon atoms.

Rc &_lt; The most preferred embodiment is a group represented by the following general formula.

In the above formula, Rc ₆ has a carbon number of 4 or less, preferably 2-4, more preferably 2 or 3 perfluoroalkyl group, or 1 to 4 fluorine atoms and / or 1 to 3 fluoro A phenylene group substituted with an alkyl group.

Ax represents a single bond or a divalent linking group (preferably -O- group, -CO ₂ - group, -S- group, SO ₃ - group or -SO ₂ N (Rd ₁ ) - group). Rd ₁ is Represents a hydrogen atom or an alkyl group, in combination with Rc ₇ may form a ring structure.

Rc ₇ is A hydrogen atom, a fluorine atom, a linear or branched alkyl group which may be substituted, a monocyclic or polycyclic cycloalkyl group which may be substituted, or an aryl group which may be substituted. The alkyl, cycloalkyl and aryl groups which may be substituted are preferably those which do not contain a fluorine atom as a substituent.

In the general formula (AN3) and _{(AN4), Rc 3, Rc} 4 And Rc ₅ each independently represents an organic group.

In the general formula (AN3) and _{(AN4), Rc 3, Rc} 4, an organic group of Rc ₅ is identical to the preferred organic groups in Rc _1.

Rc ₃ And Rc ₄ are They may be combined to form a ring.

Rc ₃ And Rc is a group A ₄ combine to form an alkylene group are listed arylene group, preferably an alkylene group having a carbon number of perfluoro 2-4. Rc ₃ And by forming a ring by combining Rc _4, and increases the acidity of the acid generated by light irradiation, it is preferred because the sensitivity is enhanced.

In the general formula (ZI), the number of carbon atoms of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.

R ₂₀₁ ~ R ₂₀₃ combines two of the dog may be to form a ring structure, may include the oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group.

R ₂₀₁ ~ R] Examples of a group formed by combining any two of the ₂₀₃ dogs alkylene group (for example, a butylene group, a pentylene group) is enumerated.

Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include groups corresponding to the following compounds (ZI-1), (ZI-2) and (ZI-3).

The compound may be a compound having a plurality of structures represented by the general formula (ZI). For example, in the compound represented by the general formula (ZI), among R ₂₀₁ to R ₂₀₃ At least one of R < ₂₀₁ > to R < ₂₀₃ > of the other compound represented by formula (ZI) May be a compound having a structure bonded to at least one of them.

It is more preferable that the component (ZI) is the compound (ZI-1), (ZI-2) or (ZI-3) described later.

The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in the general formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.

The aryl alcohol in the phosphonium compound, R ₂₀₁ ~ R to the total part of the contribution may or aryl of R ₂₀₁ ~ R _{203 203} is an aryl group, that is an alkyl or cycloalkyl may contribute other.

Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group and a naphthyl group, or a heteroaryl group such as an indole moiety and a pyrrole moiety, more preferably a phenyl group or an indole moiety. When the arylsulfonium compound has two or more aryl groups, these two or more aryl groups may be the same or different.

The alkyl group optionally present in the arylsulfonium compound is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec- - butyl groups are listed.

The cycloalkyl group optionally present in the arylsulfonium compound is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group and a cyclohexyl group.

An aryl group, alkyl group and cycloalkyl group of R ₂₀₁ ~ R ₂₀₃ is an alkyl group as each of the substituents (e.g., a carbon number of alkyl group of 1 to 15), a cycloalkyl group (e.g., a cycloalkyl group having from 3 to 15 carbon atoms), aryl groups ( (For example, an aryl group having 6 to 14 carbon atoms), an alkoxy group (e.g., an alkoxy group having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group. The substituent is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a straight, branched or cyclic alkoxy having 1 to 12 carbon atoms, an alkyl group having 1 to 4 carbon atoms, More preferably an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted on any one of R3 of ₂₀₁ ~ R _203, or may be substituted on all three dogs. When R ₂₀₁ ~ R ₂₀₃ is an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Hereinafter, the compound (ZI-2) will be described.

The compound (ZI-2) is a compound in which each of R ₂₀₁ to R ₂₀₃ in the general formula (ZI) independently represents an organic group containing no aromatic ring. The aromatic rings used herein include aromatic rings containing hetero atoms.

As R ₂₀₁ to R ₂₀₃ , an organic group not containing an aromatic ring is generally 1 to 30 carbon atoms and preferably 1 to 20 carbon atoms.

R ₂₀₁ to R ₂₀₃ each independently preferably represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear, branched or cyclic 2-oxoalkyl group or alkoxycarbonylmethyl group, Oxoalkyl group on the benzene ring.

R ₂₀₁ ~ as R ₂₀₃ alkyl groups may be either linear or branched, alkyl group a linear or branched, having 1 to 10 carbon atoms, preferably in the (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group) Do. The alkyl group of R ₂₀₁ to R ₂₀₃ is more preferably a linear or branched 2-oxoalkyl group or alkoxycarbonylmethyl group.

The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a cycloalkyl group having from 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

More preferably, the cycloalkyl group as R ₂₀₁ to R ₂₀₃ is a cyclic 2-oxoalkyl group.

As R ₂₀₁ ~ R ₂₀₃ is preferably 2-oxoalkyl group is attributed with may be one either a straight chain, branched or cyclic, in the 2-position of the alkyl group or cycloalkyl group> C = O group.

As R ₂₀₁ to R _{203, it} is preferable that the alkoxy group in the alkoxycarbonylmethyl group is an alkoxy group having 1 to 5 carbon atoms (for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

R ₂₀₁ to R ₂₀₃ each may be further substituted by a halogen atom, an alkoxy group (for example, an alkoxy group having 1 to 5 carbon atoms), a hydroxy group, a cyano group or a nitro group.

The compound (ZI-3) is a compound represented by the following general formula (ZI-3), which is a compound having a phenacylsulfonium salt structure.

In the general formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy or a halogen atom.

R _6c And R _7c each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group.

R _x And R _y each independently represent an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _7c or a pair of R _x and R _y may be bonded to each other to form a ring structure, and the ring structure may contain an oxygen atom, a sulfur atom, an ester bond or an amide bond . Examples of the groups formed by combining any two or more of R _1c to R _7c or a pair of R _x and R _y include a butylene group and a pentylene group.

X ^- is Non-nucleophilic anion, and examples thereof include those represented by the general formula (ZI) in which X ^- Is the same as the non-nucleophilic anion example.

The alkyl group as R _1c to R _7c may be either linear or branched. Examples thereof include an alkyl group having 1 to 20 carbon atoms and a linear or branched alkyl group having 1 to 12 carbon atoms (e.g., methyl, ethyl, A linear or branched propyl group, a straight chain or branched butyl group, or a linear or branched pentyl group).

The cycloalkyl group as R _1c to R _7c is preferably a cycloalkyl group having 3 to 8 carbon atoms (e.g., cyclopentyl group, cyclohexyl group).

As R _1c to R _5c , the alkoxy group may be any of linear, branched and cyclic, and includes, for example, an alkoxy group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 5 carbon atoms (for example, A methoxy group, an ethoxy group, a propoxy group, a straight chain or branched propoxy group, a straight chain or branched butoxy group, or a linear or branched pentoxy group) or a cyclic alkoxy group having 3 to 8 carbon atoms (for example, Oxy, cyclohexyloxy).

A _{compound wherein} any one of R _1c to R _5c is a linear or branched alkyl group, a cycloalkyl group or a linear, branched or cyclic alkoxy group is preferable, and a compound wherein the sum of the carbon atoms of R _1c to R _5c is 2 to 15, More preferable. By such a structure, solvent solubility is further improved, and generation of particles is inhibited during storage.

The alkyl group as R _x and R _y is the same as the alkyl group as R _1c to R _7c . The alkyl group as R _x and R _y is preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.

As the straight-chain, branched or cyclic 2-oxoalkyl group, a group having> C = O at two positions of an alkyl group or a cycloalkyl group as R _1c to R _7c is enumerated.

The alkoxy group in the alkoxycarbonylmethyl group is the same as the alkoxy group in R _1c to R _5c .

R _x and R _y are Is preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more carbon atoms, and more preferably 8 or more carbon atoms.

In the general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ independently represent an aryl group which may have a substituent, an alkyl group which may have a substituent, or a cycloalkyl group which may have a substituent.

The aryl group of R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

The alkyl group represented by R ₂₀₄ to R ₂₀₇ may be either linear or branched and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group) Do.

The cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ is preferably a cycloalkyl group having from 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

R ₂₀₄ to R ₂₀₇ are Examples of the substituent which may have a substituent include an alkyl group (for example, an alkyl group having 1 to 15 carbon atoms), a cycloalkyl group (for example, a cycloalkyl group having 3 to 15 carbon atoms), an aryl group (for example, An aryl group), an alkoxy group (e.g., an alkoxy group having 1 to 15 carbon atoms), a halogen atom, a hydroxy group, and a phenylthio group.

X ^- represents a non-nucleophilic anion and is the same as the non-nucleophilic anion of X < ^- > in formula (ZI).

As a preferable compound among the compounds capable of generating an acid upon irradiation with an actinic ray or radiation, compounds represented by the following general formulas (ZIV), (ZV) and (ZVI) are further enumerated.

In formulas (ZIV) to (ZVI), Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.

R ₂₀₈ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group.

R ₂₀₉ and R ₂₁₀ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or an electron withdrawing group. R ₂₀₉ is preferably a substituted or unsubstituted aryl group, and R ₂₁₀ is preferably an electron-withdrawing group, more preferably a cyano group or a fluoroalkyl group.

A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group.

(ZI) to (ZIII) are preferable among the compounds capable of generating an acid upon irradiation with an actinic ray or radiation, more preferably a compound represented by the general formula (ZI), and a compound represented by the general formula More preferred are compounds represented by ZI-1 to ZI-3.

Further, compounds capable of generating an acid represented by the following general formulas (AC1) to (AC3) by irradiation with an actinic ray or radiation are preferable.

That is, a preferred acid generator is a structure represented by the general formula (ZI), X ^- represents the formula (AN1), (AN3) and an anion of a compound selected from (AN4), X ^- represents the formula (AN3) and ( AN4) are more preferable.

Particularly preferred examples of compounds capable of decomposing by irradiation with an actinic ray or radiation to generate an acid are listed below.

One of these acid generators may be used alone, or two or more of them may be used in combination. When two or more kinds are used in combination, it is preferable to combine compounds capable of generating two or more kinds of organic acids having a total of two or more atoms except for hydrogen atoms.

The content of the acid generator in the composition is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 7 mass%, based on the total solid content of the negative resist composition.

[4] The quaternary ammonium salt (component (D)) represented by the general formula (2)

The alkyl group, alkenyl group, aryl group and aralkyl group represented by R ₃ to R ₆ in the general formula (2) may each have a substituent. Two or more of R ₃ to R ₆ may be bonded to form an alicyclic or aromatic ring.

Each of R ₃ to R ₆ is a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 1 to 30 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. Or a group containing a combination of these groups.

Each of these groups may have a substituent, and examples of the substituent include the same substituent as that of R ₁ in the general formula (1), and a hydroxyl group. These groups may each have a linking group such as an ether group, an ester group and an amide group.

Each of R ₃ to R ₆ is preferably a linear or branched alkyl group having 1 to 25 carbon atoms or a linear or branched alkenyl group having 1 to 25 carbon atoms, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms Is more preferable.

B ^- R ₇ --CO ₂ ^- group and R ₇ -SO ₃ ^- groups in, R ₇ is an aryl group, or having 7 to 18 carbon atoms 1-8 straight-chain or branched alkyl group, having 1 to 8 carbon atoms straight-chain or branched alkenyl group, having 6 to 18 of the on the Lt; / RTI >

B ^- is OH ^- is the group (R ₇ is preferably a 1 to 12 carbon atoms, having a carbon number of ^1-6-group, a halogen atom (e.g., chlorine, bromine, iodine, fluorine), or R ₇ -CO ₂ is a group (R ₇ represents an alkyl group having from 1 to 4 carbon ^atoms) is more preferred), and should preferably, ^OH-group, a halogen atom (e.g., chlorine, bromine, iodine, fluorine), or R ₇ -CO ₂ More preferable.

Hereinafter, preferred specific examples of the component (D) are listed, but the present invention is not limited thereto.

The content of the component (D) used in the present invention is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and more preferably 0.05 to 3% by mass relative to the total solid content of the negative resist composition desirable.

In the present invention, the quaternary ammonium salt of component (D) may be used singly or in a mixture of two or more kinds.

[5] Organic carboxylic acid (component (E)) [

As the component (E), the organic carboxylic acid is not particularly limited, and for example, a saturated or unsaturated aliphatic carboxylic acid, alicyclic carboxylic acid, oxycarboxylic acid, alkoxycarboxylic acid, ketocarboxylic acid, and aromatic carboxylic acid may all be used. Examples thereof include monovalent or polyvalent aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid, aliphatic carboxylic acids such as 1,1-cyclohexanedicarboxylic acid, Alicyclic carboxylic acids such as 2-cyclohexane dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and 1,1-cyclohexyldiacetic acid, acrylic acid, crotonic acid, isocrotonic acid, 3- Unsaturated aliphatic carboxylic acids such as butanoic acid, methacrylic acid, 4-pentenoic acid, propiolic acid, 2-butenoic acid, maleic acid, fumaric acid and acetylenecarboxylic acid, oxycarboxylic acids such as oxyacetic acid, alkoxy such as methoxyacetic acid and ethoxyacetic acid Benzoic acid, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2-hydroxy-3-nitrobenzoic acid, 3,5-dinitrobenzoic acid, 2-nitrobenzoic acid, 2,4-dinitro Benzoic acid, 2,5-dinitrobenzoic acid, 2,6-dinitrobenzoic acid, 3,5-dinitrobenzoic acid, 2-vinylbenzoic acid, 4-vinylbenzoic acid, phthalic acid, terephthalic acid, isophthalic acid, 2- Hydroxy-2-naphthoic acid, and 2-hydroxy-3-naphthoic acid. In the present invention, when a pattern is formed by using electron beams in vacuum, the organic carboxylic acid may volatilize from the surface of the resist film to contaminate the image chamber. Therefore, an organic carboxylic acid having an aromatic ring is a preferred compound. Among them, benzoic acid, 1-hydroxy-naphthoic acid and 2-hydroxy-3-naphthoic acid are more preferable.

These organic carboxylic acids may be used alone or in combination of two or more.

The blending amount of the organic carboxylic acid (E) is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.01 to 3 parts by mass, per 100 parts by mass of the alkali-soluble polymer (A).

The mixing ratio of the quaternary ammonium salt of the component (D) to the organic carboxylic acid of the component (E) is preferably from 5 to 95/95 to 5 (mass ratio), more preferably from (D) to (E) ) / (E) = 10-90 / 90-10 (mass ratio).

The negative resist composition of the present invention may further contain a known compound such as an organic basic compound containing nitrogen, a dye, a surfactant, a photodegradable basic compound and a photo-base generator as necessary. Examples of such compounds include those described in Japanese Patent Application Laid-Open No. 2002-6500.

Examples of preferred solvents used in the negative resist composition of the present invention include those described in JP-A-2003-6500. Preferable examples of the solvent include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether Ethyl acetate, isoamyl acetate, ethyl lactate, isopropyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl? -Methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, N, N-dimethylacetamide, propylene carbonate, and ethylene carbonate are enumerated in the above-mentioned Examples, and examples thereof include toluene, xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, do. These solvents may be used alone or in combination of two or more.

The solid content of the resist composition is preferably dissolved in the solvent at a solids concentration of 1 to 40 mass%, more preferably 1 to 30 mass%, and still more preferably 3 to 20 mass%.

The negative resist composition of the present invention is applied onto a substrate to form a thin film. The thickness of the coating film is preferably 0.05 to 4.0 mu m.

In the present invention, a commercially available inorganic or organic antireflection film may be used if necessary. An antireflection film may be applied to the upper resist layer. As the antireflection film, an antireflection film described in Japanese Patent Application Laid-Open No. 2002-6500 can be used.

Use forms of the negative resist composition of the present invention will be described below.

For example, in the fabrication of precision integrated circuit devices, the step of forming a pattern on a resist film may comprise forming a pattern on a substrate (e.g., a silicon / silicon dioxide film, a glass substrate, a metal substrate, a silicon nitride substrate, Coating a negative resist composition of the present invention on an antireflection film provided in advance on a substrate or on a substrate thereof, irradiating the coating film with a radiation or a live-ray as a light source directly or through a mask, and And a step of heating, developing, washing and drying the resist film, whereby a good resist pattern can be formed. In the present invention, the substrate is preferably a substrate other than silicon (hollow silicon), more preferably a substrate having a metal evaporated film or a metal containing film on its surface, and a Cr, Mo, MoSi, TaSi or oxides or nitrides thereof A substrate provided with a vapor-deposited film by Cr, Mo, MoSi, TaSi or an oxide or nitride thereof, more preferably a substrate provided with a vapor-deposited film of Cr, MoSi, TaSi or an oxide or nitride on the surface, Is further preferable.

The light source is preferably a light source that emits an electron beam or an X-ray at a wavelength of 150 to 250 nm (specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), or F2 excimer laser (157 nm)). In the present invention, an apparatus using an exposure light source that emits an electron beam or an X-ray is most preferable.

As the developer to be used for the negative resist composition of the present invention, a known developer may be used. Examples of these developers include developers described in JP-A-2002-6500.

[Examples]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention should not be construed as being limited thereto.

1. Synthesis Example of Constituent Materials

(1) an alkali-soluble polymer (component A)

Example 1 (Synthesis of Resin (29)):

(0.09 mol) of 4-acetoxystyrene and 0.8 g (0.006 mol) of 4-methoxystyrene were dissolved in 30 ml of 1-methoxy-2-propanol under stirring in a nitrogen stream, (0.056 mol) of 4-acetoxystyrene and 1.9 g (0.06 mole) of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd., trade name V- Methoxy-2-propanol solution containing 0.014 mol of 4-methoxystyrene was added dropwise at 70 占 폚 over 2 hours. After 2 hours, 50 mg of the initiator was added and further reacted for 2 hours. Then, the temperature was raised to 90 占 폚 and stirred for 1 hour. The obtained reaction solution was cooled and then poured into 1 L of ion-exchanged water with vigorous stirring to precipitate a white resin. The obtained resin was dried and then dissolved in 100 ml of methanol. Then, 25% tetramethylammonium hydroxide was added to hydrolyze the acetoxy group in the resin, and the resulting solution was neutralized with an aqueous hydrochloric acid solution to precipitate a white resin. This resin was washed with ion-exchanged water and dried under reduced pressure to obtain 11.6 g of the resin (29) of the present invention. The obtained resin was found to have a weight average molecular weight (Mw: polystyrene conversion value) of 9,200 and a molecular weight distribution (Mw / Mn) of 2.0 by measuring the molecular weight by GPC.

Hereinafter, the polymer of component (A) of the present invention is synthesized in the same manner.

(2) Synthesis of crosslinking agent (component B)

(HM-1): < EMI ID =

(Trisp-PA, a product of Honshu Chemical Industry Co., Ltd.) was added to a solution of 1- [alpha -methyl- alpha - (4-hydroxyphenyl) ethyl] -4- [ Was added to a 10% aqueous solution of potassium hydroxide to dissolve under stirring, and 60 ml of a 37% formalin aqueous solution was slowly added thereto at room temperature over 1 hour while stirring the solution. After stirring at room temperature for 6 hours, the solution was poured into a diluted sulfuric acid solution, and the formed precipitate was collected by filtration, washed thoroughly with water, and recrystallized from 30 ml of methanol to give the hydroxymethyl group-containing phenol derivative [HM- 20 g of a white powder of [1] is obtained. The purity was measured by 92% (liquid chromatography).

(MM-1): < RTI ID = 0.0 >

20 g of the hydroxy group-containing phenol derivative [HM-1] obtained in the above Synthesis Example was added to 1 L of methanol and dissolved with stirring under heating. Next, 1 ml of concentrated sulfuric acid was added to the solution, and the mixture was refluxed under heating for 12 hours. After completion of the reaction, the reaction solution was cooled, and 2 g of potassium carbonate was added thereto. The mixture was sufficiently concentrated and 300 ml of ethyl acetate was added. The obtained solution was washed with water and then concentrated to dryness to obtain 22 g of a white solid of a methoxymethyl group-containing phenol derivative [MM-1] having the structure shown below. The purity was 90%. (Measured by liquid chromatography)

In the same manner, the phenol derivatives shown below were synthesized.

2. Example

EXAMPLE 1

(1) Preparation and application of a negative resist coating solution

(Composition of Negative Resist Coating Solution)

Component (A): Resin (29) 0.40 g

Component (B): 0.12 g of crosslinking agent MM-1

Component (C): 0.05 g of acid generator C-1

Component (D): 0.002 g of ammonium salt D-1

Component (E): 0.012 g of organic carboxylic acid E-1

The coating solution composition was dissolved in 9.0 g of propylene glycol monomethyl ether acetate, and 0.001 g of PF6320 (product of OMNOVA, hereinafter abbreviated as "W-1") as a surfactant was added and dissolved therein. The obtained solution was microfiltered with a membrane filter having a pore size of 0.1 mu m to obtain a resist solution.

The resist solution was coated on a 6-inch wafer having chromium oxide vapor deposited in the same process as a shielding film used for a photomask, using Mark 8, a spin coater made by Tokyo Electron Ltd., and heated at 110 ° C for 90 seconds on a hot plate And dried to obtain a resist film having a thickness of 0.3 mu m.

(2) Preparation of Negative-type Resist Pattern

The resist film was irradiated with a pattern using an electron beam imaging apparatus (HL750, product of Hitachi, Ltd., acceleration voltage: 50 KeV). After irradiation, the substrate was heated on a hot plate at 120 DEG C for 90 seconds, immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The obtained patterns were evaluated for sensitivity, resolution, pattern profile and line edge roughness by the following methods.

(2-1) Sensitivity

The cross-sectional profile of the obtained pattern was observed using a scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.), and the exposure was defined as sensitivity when 0.15 mu m (line: space = 1: 1) was resolved.

(2-2) resolution

The resolution (the line and the space are separated and resolved) at the exposure amount representing the sensitivity is defined as the resolution.

(2-3) Pattern profile

The cross-sectional profile of the 0.15-μm line pattern at the exposure dose representing the sensitivity was observed using a scanning electron microscope (S-4300, a product of Hitachi, Ltd.), and evaluated in three steps of rectangular, slightly corroded and corroded.

(2-4) Line edge roughness

The line width was measured at arbitrary 30 points in a region of 50 mu m in the longitudinal direction of the 0.15 mu m line pattern at the dose indicating the sensitivity, and the variation was evaluated by 3 sigma.

(2-5) PED characteristics in vacuum

A wafer was set in a vacuum chamber and irradiated with an electron beam having a radiation amount indicative of the sensitivity. After the irradiation or after lapse of 3 hours, the wafer was baked (heat-treated) at 120 ° C for 90 seconds, .

A 0.15 占 퐉 line pattern obtained by baking and developing immediately after electron beam irradiation and a 0.15 占 퐉 line pattern obtained by baking and developing treatment after elapse of 3 hours after electron beam irradiation were observed with a scanning electron microscope (S-9220 manufactured by Hitachi Ltd.) ), And the difference between them was defined as the PED characteristic in vacuum.

The results of Example 1 were good: sensitivity: 6.0 占 폚 / cm2, resolution: 0.11 占 퐉, pattern profile: rectangular, line edge roughness: 6.0 nm, and PED characteristics in vacuum: 2.0 nm.

[Examples 2 to 16]

A resist solution and a negative pattern were formed in the same manner as in Example 1 except that each component shown in Table 1 was used. In Table 1, the ratio when two or more components are used is a mass ratio. The evaluation results are shown in Table 2 below.

[Comparative Example 1]

A resist solution and a negative pattern were formed in the same manner as in Example 1 except that the organic carboxylic acid of the component (E) shown in Table 1 was not used. The evaluation results are shown in Table 2.

[Comparative Example 2]

Preparation of a resist solution and formation of a negative pattern were carried out in the same manner as in Example 1 except that novolac resin having no repeating unit represented by the general formula (1) was used as the resin of the component (A) shown in Table 1. The evaluation results are shown in Table 2.

[Comparative Examples 3 and 4]

Preparation of a resist solution and formation of a negative pattern were carried out in the same manner as in Example 1 except that only the known nitrogen-containing organic basic compound was used without using the quaternary ammonium salt of the component (D) shown in Table 1. The evaluation results are shown in Table 2.

Hereinafter, abbreviations in the tables will be described.

(Crosslinking agent)

The acid generators used in Table 1 are as follows.

C-1: Triphenylsulfonium nonafluorobutanesulfonate

C-2: Triphenylsulfonium pentafluorobenzenesulfonate

C-3: Triphenylsulfonium-2,4-dimethylbenzenesulfonate

C-4: Bisphenyl-4-cyclohexylphenylsulfonium pentafluorobenzenesulfonate

The organic carboxylic acid used in Table 1 is as follows.

E-1: benzoic acid

E-2: 2-Naphthoic acid

E-3: 2-Hydroxy-3-naphthoic acid

E-4:? -Hydroxybenzoic acid

The other ingredients used in Table 1 are as follows. (All manufactured by Tokyo Kasei Kogyo Co., Ltd.)

F-1: 2,4,5-triphenylimidazole

F-2: 4-Dimethylaminopyridine

F-3: Triethylamine

G-1: Trimethylammonium hydrochloride

The solvents used in Table 1 are as follows.

S-1: Propylene glycol monomethyl ether acetate

S-2: Propylene glycol monomethyl ether

The surfactants used in Table 1 are as follows.

W-1: PF6320 (product of OMNOVA)

W-2: Megafac F176 (manufactured by Dainippon Ink & Chemicals, Inc.)

From Table 2, it can be seen that the negative resist composition of the present invention is excellent in sensitivity, resolution, pattern profile, line edge roughness and PED property in vacuum, and good performance is secured.

According to the present invention, it is possible to provide a negative resist composition excellent in sensitivity, resolution, pattern profile, line edge roughness and PED property in vacuum, and a pattern forming method using the composition.

The entire disclosure of the individual and all foreign patent applications which claim the benefit of alleged foreign priority claims in this specification is hereby incorporated by reference in its entirety.

Claims (8)

A vapor-deposited film is formed on a surface of a substrate, and a layer containing a negative resist composition is formed on the vapor-deposited film.
Wherein the vapor-deposited film is formed of Cr, Mo, MoSi, TaSi, an oxide thereof, or a nitride thereof,
The negative resist composition
(A) an alkali-soluble polymer containing a repeating unit represented by the general formula (1);
(B) a crosslinking agent capable of crosslinking with the alkali-soluble polymer (A) under the action of an acid;
(C) a compound capable of generating an acid upon irradiation with an actinic ray or radiation;
(D) a quaternary ammonium salt represented by the following general formula (2); And
(E) contains an organic carboxylic acid,
The mass ratio of said quaternary ammonium salt (D) and the said organic carboxylic acid (E) is 10-90: 90-10, The laminated body characterized by the above-mentioned.
In general formula (1):

R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group or an alkylcarbamoyl group, And n represents an integer of 1 to 3.)
General formula (2):

(R ₃ ~ R ₆ are each independently an alkyl group, an alkenyl group, an aryl group or an aralkyl group; B ^- is OH ^- group, a halogen atom, R ₇ -CO ₂ ^- group or an R ₇ -SO ₃ ^- group; And R < ₇ > represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. The method according to claim 1,
Wherein the crosslinking agent (B) is a phenol compound containing two or more benzene rings in the molecule and not containing a nitrogen atom. Forming a laminate according to claim 1; And
And exposing and developing the layer containing the negative resist composition. The method according to claim 1,
Wherein the alkali-soluble polymer (A) further contains at least one repeating unit selected from the repeating units represented by the general formulas (3), (4) and (5).
The general formula (3)

In general formula (4):

The general formula (5)

(

Represents any group selected from the following structures.

(Wherein A has the same meaning as A in the formula (1), X represents a single bond, -COO- group, -O- group or -CON (R ₁₆ ) - group, R ₁₆ represents a hydrogen atom or an alkyl group R ₁₁ to R ₁₅ each independently represent the same meaning as R _{1 in} Formula (1); R ₁₀₁ to R ₁₀₆ each independently represent a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkyl An alkenyl group, an aryl group, an aralkyl group or a carboxy group; a to f each independently represent an integer of 0 to 3.) The method according to claim 1,
The crosslinking agent (B) is a phenol derivative having a molecular weight of 1,200 or less, 3 to 5 benzene rings in the molecule, and 2 or more hydroxymethyl groups or alkoxymethyl groups in total, wherein the two or more hydroxymethyl groups or alkoxymethyl groups Is intensively bonded to at least one of the benzene rings or is dispersed and bound to the benzene ring. The method according to claim 1,
The organic carboxylic acid (E) is at least one member selected from the group consisting of saturated or unsaturated aliphatic carboxylic acid, alicyclic carboxylic acid, oxycarboxylic acid, alkoxycarboxylic acid, ketocarboxylic acid and aromatic carboxylic acid. The method according to claim 6,
The organic carboxylic acid (E) is at least one member selected from the group consisting of benzoic acid, 1-hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid. The method according to claim 1,
The quaternary ammonium salt (D) is contained 0.05 to 3% by mass based on the total solids of the negative resist composition, and the organic carboxylic acid (E) is contained by 0.01 to 3% by mass relative to the total solids of the negative resist composition Laminate.