JP2009244805A - Positive resist composition and pattern formation method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemically amplified positive resist composition which has high sensitivity and high resolution, is excellent in focal depth width characteristic and storage stability of a resist solution and allows formation of a resist pattern excellent in profile shape without substrate dependence, and is sensitive to excimer laser of KrF or the like, and radiation such as X ray and electron beam. <P>SOLUTION: The positive resist composition comprises: a compound (A) which produces carboxylic acid represented by the formula (I) by irradiation with active light rays or radiation; a resin (B) which is an alkali-insoluble or alkali-hardly soluble resin protected by acid-decomposable group and becomes alkali-soluble when the acid-decomposable group is decomposed; and a compound (C) which produces an acid other than the acid represented by the formula (I) by irradiation with active light ray or radiation. In the formula (I), R<SB>1</SB>and R<SB>2</SB>respectively and independently present a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl group, an alkenyl group or an allyl group. The alkyl group, cycloalkyl group, alkenyl group and allyl group may have a substituent respectively. Further, R<SB>1</SB>and R<SB>2</SB>may be coupled to each other to form a ring. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a chemically amplified positive resist composition that is sensitive to radiation such as excimer lasers such as ultraviolet rays, far ultraviolet rays, and KrF, X-rays, and electron beams.

  Conventionally, in a manufacturing process of a semiconductor device such as an IC or LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Accordingly, there is a tendency for the exposure wavelength to be shortened from g / i line to KrF excimer laser light.

  As a resist suitable for a lithography process using KrF excimer laser light, electron beam, or EUV light, a chemically amplified resist utilizing an acid-catalyzed reaction is mainly used from the viewpoint of high sensitivity. Is a phenolic polymer (hereinafter abbreviated as “phenolic acid-decomposable resin”) having a property that is insoluble or hardly soluble in an alkali developer and becomes soluble in an alkali developer by the action of an acid, and A chemically amplified resist composition comprising an acid generator is effectively used.

  With respect to these positive resists, several resist compositions using a phenolic acid-decomposable resin copolymerized with an acid-decomposable acrylate monomer have been known so far. For example, a positive resist composition disclosed in Patent Document 1 can be used.

  Further, Patent Document 2 proposes to use an acid generator comprising a combination of “a compound that generates a carboxylic acid having a boiling point of 150 ° C. or higher upon irradiation” and “a compound that generates an acid other than a carboxylic acid”. Has been. As described above, many improvements have been made from the viewpoint of resins, acid generators, etc., and they have been put into practical use.

However, chemically amplified resists utilizing such acid-catalyzed reactions are more substrate-dependent than conventional positive photoresists based on alkali-soluble novolak resins and quinonediazide group-containing compounds, especially TiN. Basic substrates such as SiN and SiON have a drawback in that when a resist pattern is actually formed, a bottom pattern is formed, and a desirable rectangular pattern is not formed.
US Pat. No. 5,561,194 Japanese Patent No. 3991462

  The object of the present invention is to solve the problem of performance improvement technology in microfabrication of semiconductor elements using actinic rays or radiation, in particular KrF excimer laser light, electron beam or EUV light, and has high sensitivity and high resolution. And excels in excimer lasers such as KrF, X-rays, and electron beams that are capable of forming resist patterns with excellent substrate profile and excellent profile shape. It is an object of the present invention to provide a sensitive chemical amplification type positive resist composition.

As a result of intensive studies, the present inventors have achieved the object of the present invention by the following configuration.
(1) (A) a compound that generates a carboxylic acid represented by the following formula (I) by irradiation with actinic rays or radiation,
(B) an alkali-insoluble or hardly-alkali-soluble resin protected with an acid-decomposable group, which becomes alkali-soluble when the acid-decomposable group is decomposed; and (C) by irradiation with actinic rays or radiation. A positive resist composition comprising a compound that generates an acid other than the carboxylic acid represented by formula (I).

In formula (I),
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and these groups may have a substituent. R ₁ and R ₂ may be bonded to each other to form a ring.

(2) The positive resist composition as described in (1) above, wherein the resin (B) contains repeating units represented by the following formulas (II), (III) and (IV).

In formulas (II) to (IV),
A represents a group that decomposes and leaves by the action of an acid.
R ₃ each independently represents a hydrogen atom or a methyl group.
R ₄ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms containing a halogen atom and / or an oxygen atom. Represents a phenyl group, an aralkyl group, a carbamoyl group, a cyano group, or a nitro group.
m represents 1 or 2.
n represents an integer of 0 to 2.
(3) The positive resist composition as described in (2) above, wherein the repeating unit represented by the formula (II) has a structure represented by the formula (II) -a.

(4) The positive resist composition as described in (2) or (3) above, wherein the repeating unit represented by the formula (III) has a structure represented by the formula (III) -a.

In Formula (III) -a, R ₃ is a hydrogen atom or a methyl group.
(5) The positive resist composition as described in any one of (1) to (4) above, wherein the resin (B) has a mass average molecular weight of 15,000 to 25,000.

(6) The positive resist composition as described in any one of (1) to (5) above, further comprising (D) a nitrogen-containing organic basic compound.
(7) The positive resist composition as described in any one of (1) to (6) above, further comprising (E) a surfactant.
(8) The positive resist composition as described in any one of (1) to (7) above, further comprising a solvent.
(9) The positive resist composition as described in (8) above, which contains propylene glycol monomethyl ether acetate as a solvent.
(10) The positive resist composition as described in (9) above, further containing propylene glycol monomethyl ether as the solvent.
(11) A pattern forming method comprising a step of forming a resist film using the positive resist composition according to any one of (1) to (10), exposing and developing the resist film.

Hereinafter, the compounds used in the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[1] Carboxylic acid generator (A)
The positive resist composition of the present invention contains a compound that generates a carboxylic acid represented by the general formula (I) upon irradiation with actinic rays or radiation (hereinafter also referred to as “carboxylic acid generator (A)”).

In formula (I),
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and the alkyl group, cycloalkyl group, alkenyl group and aryl group have a substituent. May be. R ₁ and R ₂ may be bonded to each other to form a ring.

  Examples of the substituent that the alkyl group, cycloalkyl group, and alkenyl group may have include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), aryl group (phenyl group, naphthyl group, etc.), hydroxy group, An alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), a cyano group, a nitro group, etc. can be mentioned.

  Examples of the substituent that the aryl group may have include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), nitro group, cyano group, alkyl group (methyl group, ethyl group, t-butyl group, t -Amyl group, octyl group etc.), hydroxy group, alkoxy group (methoxy group, ethoxy group, butoxy group etc.), cyano group, nitro group and the like.

R ₁ and R ₂ are preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or 6 to 24 carbon atoms. An aryl group, more preferably a fluorine atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and particularly preferably a fluorine atom or a carbon atom. These are an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 15 carbon atoms. Each of these groups may have a substituent.
In the following, preferred specific examples of the carboxylic acid represented by the formula (I) generated by irradiation with actinic rays or radiation are listed, but of course not limited thereto.

The carboxylic acid generator (A) is preferably a compound represented by the following general formula (A).

In general formula (A), R _{21 to} R ₂₃ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and these groups may have a substituent. Z represents a sulfur atom or an iodine atom. When Z is a sulfur atom, p is 1, and when Z is an iodine atom, p is 0. R ₁ and R ₂ are the same as those in the general formula (I).

Examples of the substituent that the alkyl group, cycloalkyl group, and alkenyl group may have in the above atomic group include those exemplified as the substituents when R ₁ and R ₂ are alkyl groups. The same can be mentioned. As an example of the substituent of an aryl group, the same thing as what was mentioned as an example of a substituent in case the said R < ₁ > and R < ₂ > are aryl groups is mentioned.

R _{21 to} R ₂₃ are preferably each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms. And more preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 18 carbon atoms, and particularly preferably an aryl group having 6 to 15 carbon atoms. . Each of these groups may have a substituent.

Z represents a sulfur atom or an iodine atom. p is 1 when Z is a sulfur atom, and 0 when Z is an iodine atom.
In addition, two or more cation moieties of the formula (A) are bonded by a single bond or a linking group (for example, -S-, -O-, etc.) to form a cation structure having a plurality of cation moieties of the formula (A). May be.
Moreover, it is preferable that both R ₁ and R ₂ are fluorine atoms or fluorine atom-containing groups.

Although the preferable specific example of the compound (A) which generate | occur | produces carboxylic acid by irradiation of actinic light or a radiation below is given, of course, it is not limited to these.

  The content of the carboxylic acid generator (A) in the positive resist composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.1 to 10% by mass, based on the total solid content of the composition. 5 mass%, particularly preferably 0.1 to 3 mass%. Moreover, the compound which generate | occur | produces the carboxylic acid represented by general formula (I) by irradiation of these actinic rays or radiation may use 1 type, and may mix and use 2 or more types.

[2] Resin (B)
The resist composition of the present invention is an alkali-insoluble or alkali-insoluble resin protected with an acid-decomposable group, and becomes an alkali-soluble resin when the acid-decomposable group is decomposed by the action of an acid ( Hereinafter, it is also referred to as “resin (B)”.
The resin (B) of the present invention is a group (hereinafter referred to as “acid-decomposable group”) that is decomposed by the action of an acid to generate an alkali-soluble group in the main chain or side chain of the resin, or in both the main chain and the side chain. Resin).

  Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) Imido group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group A group having

  Preferred alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.

  A preferred group as an acid-decomposable group (acid-decomposable group) is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.

Examples of the group capable of leaving with an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.
The resin (B) of the present invention more preferably contains repeating units represented by the following formulas (II), (III), and (IV).

In the formulas (II) to (IV), A represents a group that decomposes and leaves by the action of an acid. R ₃ each independently represents a hydrogen atom or a methyl group. R ₄ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms containing a halogen atom and / or an oxygen atom. Represents a phenyl group, an aralkyl group, a carbamoyl group, a cyano group, or a nitro group. m represents 1 or 2, and n represents an integer of 0 to 2.

The preferable composition ratio in the resin (B) of the repeating unit represented by the formula (II) is 5 to 75 mol%, more preferably 20 to 70 mol% with respect to all the repeating units in the resin (B). is there.
It is preferable that the repeating unit represented by the formula (II) is contained in the above range from the viewpoint of achieving both the adhesion to the substrate and the resolution.
Hereinafter, although the specific structure of the repeating unit represented by Formula (II) is illustrated, it is not this limitation.

It is particularly preferable that the repeating unit represented by the general formula (II) has a structure represented by the formula (II) -a.

  A in the repeating unit represented by the formula (III) represents a group that decomposes and leaves by the action of an acid, and is preferably a hydrocarbon group (preferably having a carbon number of 20 or less, more preferably 4 to 12). , A t-butyl group, a t-amyl group, a hydrocarbon group having an alicyclic structure (for example, an alicyclic group itself, or a group in which an alicyclic group is substituted on an alkyl group), more preferably a t-butyl group. Is preferred. The alicyclic structure may be monocyclic or polycyclic. Specific examples include monocyclo, bicyclo, tricyclo, and tetracyclo structures having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These hydrocarbon groups having an alicyclic structure may further have a substituent. Further, examples of the substituent that may be included include an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, an alkoxycarbonyl group, a carbamoyl group, a cyano group, and a nitro group.

  The preferable composition ratio in the resin (B) of the repeating unit represented by the formula (III) is 5 to 50 mol%, more preferably 10 to 40 mol%, based on all the repeating units in the resin (B). is there.

Setting the content of the repeating unit represented by the formula (III) in the above range is preferable from the viewpoint of achieving both a dissolution rate in an alkali developer and plasma etching resistance.
Hereinafter, although the specific structure of the repeating unit represented by Formula (III) is illustrated, it is not this limitation.

It is particularly preferable that the repeating unit represented by the general formula (III) has a structure represented by the formula (III) -a.

In formula (III) -a, _{R 3} has the same meaning as _{R 3} in formula (III), represents a hydrogen atom or a methyl group.

R ₄ in the repeating unit represented by the formula (IV) is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, an alkoxyl group, an alkoxycarbonyl group, a carbamoyl group, a cyano group, or a nitro group. And so on.

The preferable composition ratio in the resin (B) of the repeating unit represented by the formula (IV) is 1 to 50 mol%, more preferably 2 to 40 mol%, more preferably 2 to 2 mol based on the resin (B). 35 mol%. Setting the repeating unit represented by the formula (IV) within the above range is preferable for obtaining sufficient rectangular etching pattern due to sufficient plasma etching resistance and dissolution inhibiting effect while achieving sufficient solubility in the exposed area. .
Hereinafter, although the specific structure of the repeating unit represented by Formula (IV) is illustrated, it is not this limitation.

  The mass average molecular weight (Mw) of the resin (B) is preferably 10,000 or more. By increasing the molecular weight, the alkali dissolution rate in the unexposed area can be reduced. Therefore, the protection rate can be lowered, and various performances such as etching resistance and DOF margin of isolated lines are improved.

The mass average molecular weight (Mw) is preferably 200,000 or less from the viewpoint of the dissolution rate of the resin itself in alkali, sensitivity, and defect generation.
The dispersity (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and particularly preferably 1.0 to 2.0.

Among them, the mass average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 200,000, more preferably in the range of 10,000 to 100,000, and particularly preferably 12,000. It is in the range of ˜50,000, and most preferably in the range of 15,000 to 25,000.
Here, the mass average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  The content of the resin (B) in the positive resist composition is preferably 75 to 99 mass%, more preferably 90 to 98 mass%, based on the total solid content of the composition.

Resin (B) can synthesize | combine resin (B) with a dispersion degree of 1.5-2.0 by performing radical polymerization using a radical polymerization initiator. Further preferred resin (B) having a dispersity of 1.0 to 1.5 can be synthesized by living radical polymerization.
Although the specific example of resin (B) is shown below, it is not limited to these.

[3] Acid generator (C)
The resist composition of the present invention comprises (C) a compound that generates an acid other than the carboxylic acid represented by the general formula (I) upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator (C)”). Containing. As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, or irradiation with actinic ray or radiation used for micro-resist etc. Known compounds that generate acids and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. No. 3914407, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, The compounds described in JP-A-62-153853 and JP-A-63-146029 can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712, etc. can also be used.

Compounds represented by the following general formulas (ZI), (ZII), and (ZIII) as preferred compounds among the compounds capable of decomposing upon irradiation with actinic rays or radiation as the acid generator (C) Can be mentioned.

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion, preferably a sulfonate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{− and the} like, preferably Is an organic anion containing a carbon atom. Preferable organic anions include organic anions represented by the following formulas AN1 to AN3.

In the formula _AN1~AN3, Rc 1 ~Rc ₃ each independently represents an organic group. Examples of the organic group in Rc _{1 to} Rc ₃ include those having 1 to 30 carbon atoms, and preferably an optionally substituted alkyl group, aryl group, or a plurality of these are a single bond, —O—, —CO. _{2 -, - S -, -} SO 3 -, - SO 2 N (Rd 1) - it can be exemplified linked group a linking group such as. Further, it may form a ring structure with another bonded alkyl group or aryl group.
Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with the bonded alkyl group or aryl group.

The organic group of Rc _{1 to} Rc ₃ may be an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with 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 Rc _{1 to} Rc ₃ have 5 or more carbon atoms, it is preferable that at least one carbon atom is substituted with a hydrogen atom, and it is more preferable that the number of hydrogen atoms is larger than that of fluorine atoms. By not having a perfluoroalkyl group having 5 or more carbon atoms, ecotoxicity is reduced.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.
Further preferred examples of the component (Z1) include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.
Arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group with the remaining being an alkyl group.

  Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, and an aryldialkylsulfonium compound.

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

  The alkyl group that the arylsulfonium compound has as necessary is preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec. -Butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like can be mentioned.

Aryl group of R ₂₀₁ to R _203, an alkyl group, an alkyl group (for example, 1 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, You may have a hydroxyl group and a phenylthio group as a substituent. Preferred substituents are linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, most preferably alkyl groups having 1 to 4 carbon atoms, It is a C1-C4 alkoxy group. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

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

Compound (ZI-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group containing no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group, more preferably a linear, branched, or cyclic 2-oxoalkyl group, An alkoxycarbonylmethyl group, most preferably a straight-chain and branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be linear, branched, or cyclic, preferably a linear or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group) and cyclic alkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).

The 2-oxoalkyl group as R _{201 to} R ₂₀₃ may be linear, branched or cyclic, and preferably includes a group having> C═O at the 2-position of the above alkyl group. it can.

The alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R _203, preferably may be mentioned alkoxy groups having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Two members out of R _{201 to} R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

Next, the compound (ZI-3) will be described.
The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.

R _6c and R _7c represent a hydrogen atom or an alkyl group.

  Rx and Ry each independently represents an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _7c may be bonded to form a ring structure. R _x and R _y may combine to form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond.

  X- has the same meaning as X- in formula (ZI).

The alkyl group as R _{1c to} R _7c may be linear, branched or cyclic, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms. Group (for example, methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group), C3-C8 cyclic alkyl group (for example, cyclopentyl group, cyclohexyl group) ).

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Preferably either a straight chain of R _1c to R _5c, branched, cyclic alkyl group, or a linear, branched or cyclic alkoxy group, more preferably the sum of the carbon atoms of R _5c from R _1c 2 to 15 It is. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save. R _6c and R _7c are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

_Examples of the alkyl group as R _x and R _y include the same alkyl groups as those described for R _{1c to} R _7c .
Examples of the 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group _exemplified for R _{1c to} R _7c .
Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R _{1c to} R _5c .
Examples of the group formed by combining R _x and R _y include a butylene group and a pentylene group.
R _x and R _y are preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

Next, general formulas (ZII) and (ZIII) will be described.
In general formulas (ZII) and (ZIII), R _{204 to} R ₂₀₇ each independently have an aryl group which may have a substituent, an alkyl group which may have a substituent, or a substituent. Represents an optionally substituted cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group.
The alkyl group as R ₂₀₄ to R ₂₀₇ may be linear or branched, preferably a linear or branched alkyl group (e.g. having 1 to 10 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group Etc.).

The cycloalkyl group as R ₂₀₄ to R ₂₀₇ may be exemplified a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group, etc. norbornyl).

The R ₂₀₄ to R ₂₀₇ are substituents which may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), an aryl group (e.g. having 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms ), Halogen atoms (fluorine atoms, chlorine atoms, etc.), hydroxyl groups, phenylthio groups, and the like.
X ⁻ has the same meaning as the non-nucleophilic anion of X ^{− in} formula (ZI).

Among the compounds capable of generating an acid upon irradiation with actinic rays or radiation as the acid generator (C), compounds represented by the following general formulas (ZIV), (ZV) and (ZVI) are further included. Can be mentioned.

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents a substituted or unsubstituted aryl group.
R ₂₀₈ independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group in the general formulas (ZV) and (ZVI). From the viewpoint of increasing the strength of the generated acid, R ₂₀₈ is preferably substituted with a fluorine atom.

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. 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.
A compound having a plurality of structures represented by the general formula (ZVI) is also preferred in the present invention. For example, either R ₂₀₉ or R ₂₁₀ of the compound represented by the general formula (ZVI) has a structure bonded to either R ₂₀₉ or R ₂₁₀ of another compound represented by the general formula (ZVI). It may be a compound.

Among the compounds that decompose as a result of irradiation with actinic rays or radiation as the acid generator (C), more preferred are compounds represented by the general formulas (ZI) to (ZIII), even more preferred. Is a compound represented by (ZI), most preferably a compound represented by (ZI-1) to (ZI-3).
Furthermore, the compound which generate | occur | produces the acid represented by the following general formula AC1-AC3 by irradiation of actinic light or a radiation is preferable.

That is, the most preferred embodiment of the component (C) is a compound in which X- is an anion selected from AN1, AN2, and AN3 in the structure of the general formula (ZI). Rc ₁ to Rc ₃ are each the same as _Rc 1 to Rc ₃ in the above formula AN1, AN2, AN3.
Specific examples of the acid generator (C) are shown below, but are not limited thereto.

An acid generator (C) can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms other than hydrogen atoms by two or more.
The content of the acid generator (C) in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 based on the total solid content of the resist composition. -7% by mass.

[4] Organic basic compound (D)
The resist composition of the present invention preferably contains an organic basic compound. The organic basic compound is preferably a compound that is more basic than phenol. The molecular weight of the organic basic compound is usually 100 to 900, preferably 150 to 800, more preferably 200 to 700. Further, nitrogen-containing basic compounds are particularly preferable.
Preferred nitrogen-containing basic compounds are compounds having structures of the following formulas (CI) to (CV) as a preferred chemical environment. Formulas (CII) to (CV) may be part of a ring structure.

Here, R ₂₅₀ , R ₂₅₁ and R ₂₅₂ may be the same or different and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group. (Preferably having 6 to 20 carbon atoms), wherein R ₂₅₁ and R ₂₅₂ may be bonded to each other to form a ring.

The alkyl group may be unsubstituted or may have a substituent. Examples of the alkyl group having a substituent include an aminoalkyl group having 1 to 6 carbon atoms and a hydroxyalkyl group having 1 to 6 carbon atoms. preferable.
R ₂₅₃ , R ₂₅₄ , R ₂₅₅ and R ₂₅₆ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms.

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

  Further, at least one nitrogen-containing compound selected from an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group can be exemplified. .

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably C6-C12) may be bonded to a nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group. Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. As the halogen atom, chloride, bromide, and iodide are particularly preferable. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Etc. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be any in the range of 1 to 5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  The amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. Then, it can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform. Alternatively, after reacting by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the end, an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium is added, and then ethyl acetate, It can be obtained by extraction with an organic solvent such as chloroform.

  In the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group, the sulfonic acid ester group may be any of alkyl sulfonic acid ester, cycloalkyl group sulfonic acid ester, and aryl sulfonic acid ester. In the case of an alkyl sulfonate ester, the alkyl group has 1 to 20 carbon atoms, in the case of a cycloalkyl sulfonate ester, the cycloalkyl group has 3 to 20 carbon atoms, and in the case of an aryl sulfonate ester, the aryl group has 6 carbon atoms. ~ 12 are preferred. Alkyl sulfonic acid ester, cycloalkyl sulfonic acid ester, and aryl sulfonic acid ester may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, and a sulfonic acid. An ester group is preferred.

It is preferable to have at least one oxyalkylene group between the sulfonate group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  Preferred nitrogen-containing basic compounds include guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and the like. It is done. These may have a substituent, and preferred substituents include 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 and the like.

  Particularly preferred nitrogen-containing basic compounds include 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-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4-aminoethylpyridine, 3-amino Loridine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-imino Piperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methyl Pyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,8-diazabicyclo [5 4.0] -7-undecene, but is not limited thereto.

  A tetraalkylammonium salt type nitrogen-containing basic compound can also be used. Of these, tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.) is particularly preferable. These nitrogen-containing basic compounds are used alone or in combination of two or more.

  The use ratio of the acid generator (C) and the nitrogen-containing basic compound in the composition is preferably nitrogen-containing basic compound / acid generator (C) (molar ratio) = 0 to 10. That is, the molar ratio is preferably 10 or less from the viewpoint of sensitivity and resolution. The nitrogen-containing basic compound / acid generator (C) (molar ratio) is more preferably 0 to 5, and still more preferably 0 to 3.

[5] Surfactant (E)
In the present invention, surfactants can be used, which are preferable from the viewpoints of film-forming properties, pattern adhesion, development defect reduction, and the like.

  Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, F173 (manufactured by Dainippon Ink and Chemicals), Florad FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants, organosilanes Hexane polymer KP341 (manufactured by Shin-Etsu Chemical Co.) and acrylic or methacrylic acid-based (co) polymer Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.). The blending amount of these surfactants is usually 2 parts by mass or less, preferably 1 part by mass or less, per 100 parts by mass of the solid content in the composition of the present invention.

  These surfactants may be added alone or in some combination.

  The surfactant is any one of fluorine and / or silicon surfactants (fluorine surfactants and silicon surfactants, surfactants containing both fluorine atoms and silicon atoms), or It is preferable to contain 2 or more types.

  As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540 No. 7, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A 2002-277862, US Pat. No. 5,405,720. , No. 5,360,692, No. 5,529,881, No. 5,296,330, No. 5,543,098, No. 5,576,143, No. 5,294,511, No. 5,824,451. The following commercially available surfactants can also be used as they are.

  Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

  As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block linked body) or a poly (block linked body of oxyethylene and oxypropylene) group, may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Coalesce, etc. Can.

  The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total solid content of the positive resist composition.

[6] Solvent The resist composition of the present invention is dissolved in a solvent that dissolves each of the above components and coated on a support. The solid content concentration of all resist components is usually preferably 2 to 30% by mass, more preferably 3 to 25% by mass.

  Solvents that can be used here include 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- Preferred are dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like. Germany or as a mixture thereof may be used.

  As a solvent, it is preferable to contain propylene glycol monomethyl ether acetate. Furthermore, it is more preferable to contain propylene glycol monomethyl ether.

[7] Other additives The positive resist composition of the present invention may further contain a photobase generator and the like, if necessary.

1. Photobase generators Photobase generators that can be added to the composition of the present invention include JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, JP-A-5-5995, and JP-A-6. -194834, 8-146608, 10-83079, and European Patent 622682, specifically, 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl Cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide, 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate and the like can be preferably used. These photobase generators are added for the purpose of improving the resist shape and the like.

2. Antioxidant The resist composition of the present invention may contain an antioxidant.
The antioxidant is for preventing the organic material from being oxidized in the presence of oxygen.

  The antioxidant is not particularly limited as long as it is effective in preventing the oxidation of commonly used plastics, for example, a phenolic antioxidant, an antioxidant made of an organic acid derivative, and a sulfur-containing agent. Examples thereof include antioxidants, amine-based antioxidants, antioxidants composed of amine-aldehyde condensates, and antioxidants composed of amine-ketone condensates. Of these antioxidants, phenol antioxidants and antioxidants composed of organic acid derivatives are used as antioxidants in order to exhibit the effects of the present invention without reducing the function of the resist. Is preferred.

  Here, as the phenolic antioxidant, substituted phenols such as 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-tert-butylphenol, 2,6-di-tert- Butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, butyl hydroxyanisole, 2- (1-methyl (Cyclohexyl) -4,6-dimethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2-methyl-4,6-dinonylphenol, 2,6-di-tert-butyl-α-dimethylamino- p-cresol, 6- (4-hydroxy-3,5-di-tert-butylanilino) 2,4-bisoctyl-thio-1,3,5-triazine, n-octyl Decyl-3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, octylated phenol, aralkyl-substituted phenols, alkylated p-cresol, hindered phenol, etc. Bis, tris, polyphenols such as 4,4′-dihydroxy diphenyl, methylene bis (dimethyl-4,6-phenol), 2,2′-methylene-bis- (4-methyl-6-tert. -Butylphenol), 2,2'-methylene-bis- (4-methyl-6-cyclohexyl phenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4 '-Methylene-bis- (2,6-di-tert-butylphenol), 2,2'-methylene-bis- (6-alphamethyl-benzyl- -Cresol), methylene-bridged polyvalent alkylphenol, 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2 ' -Dihydroxy-3,3'-di- (α-methylcyclohexyl) -5,5'-dimethyl diphenylmethane, alkylated bisphenol, hindered bisphenol, 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis- [methylene-3- (3 ′, 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane and the like.

  Preferable specific examples of the antioxidant that can be used in the present invention include 2,6-di-t-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, and 2,2′-. Methylenebis (4-methyl-6-tert-butylphenol), butylhydroxyanisole, t-butylhydroquinone, 2,4,5-trihydroxybutyrophenone, nordihydroguaiaretic acid, propyl gallate, octyl gallate, lauryl gallate And isopropyl citrate. Of these, 2,6-di-t-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, butylhydroxyanisole, and t-butylhydroquinone are preferred, and 2,6-diethyl is further preferred. -T-Butyl-4-methylphenol or 4-hydroxymethyl-2,6-di-t-butylphenol is more preferred.

  The content of the antioxidant is preferably 1 ppm or more, more preferably 5 ppm or more, still more preferably 10 ppm or more, based on the total solid content of the chemically amplified resist composition, It is still more preferably 50 ppm or more, still more preferably 100 ppm or more, and particularly preferably 100 to 10,000 ppm. A plurality of antioxidants may be mixed and used.

[8] Film Formation The positive resist composition of the present invention is applied onto a substrate such as SiO ₂ (oxide film), polysilicon, SiN, SiON, TiN, basic organic antireflection film and the like to form a thin film. The thickness of this coating film is preferably 0.05 to 4.0 μm.

  Further, an antireflection film may be provided under the resist. As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. Examples of the organic antireflection film include a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in Japanese Patent Publication No. 7-69611, an alkali-soluble resin, and a light absorber, and an anhydrous maleate described in US Pat. No. 5,294,680. A reaction product of an acid copolymer and a diamine type light absorbent, a resin binder described in JP-A-6-188631, and a methylolmelamine thermal crosslinking agent, a carboxylic acid group and an epoxy described in JP-A-6-118656 An acrylic resin type antireflection film having a group and a light-absorbing group in the same molecule, a composition comprising methylol melamine and a benzophenone-based light-absorbing agent described in JP-A-8-87115, and a polyvinyl alcohol resin described in JP-A-8-179509 The thing etc. which added the low molecular light absorber are mentioned.

  In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

  Furthermore, if necessary, an antireflection film can be used as an upper layer of the resist.

  Examples of the upper antireflection film include AQUATAR-II, AQUATAR-III, and AQUATAR-VII manufactured by AZ Electronic Materials.

In the manufacture of precision integrated circuit elements, etc., the pattern formation process on the resist film is performed by a substrate (eg, SiO ₂ (oxide film), polysilicon, SiN, SiON, TiN, basic organic antireflection film, glass substrate, ITO substrate). The positive resist composition of the present invention is coated on a quartz / chromium oxide-coated substrate, etc. to form a resist film, and then irradiated with actinic rays or radiation such as KrF excimer laser light, electron beam, EUV light, etc. A good resist pattern can be formed by heating, developing, rinsing and drying.

  Examples of the alkaline developer used in development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, An aqueous solution (usually 0.1 to 20% by mass) of an alkali such as a quaternary ammonium salt such as choline or a cyclic amine such as pyrrole or piperidine can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution.

Among these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.
The pH of the alkali developer is usually 10-15.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, the content of this invention is not limited by this.
(Synthesis Example 1) Synthesis of Polymer (B-3-2) 600 g of ethylene glycol monoethyl ether acetate was placed in a 2 L flask, and nitrogen substitution was performed at a flow rate of 100 mL / min for 1 hour. In addition, 105.4 g (0.65 mol) of 4-acetoxystyrene, 35.6 g (0.25 mol) of t-butyl methacrylate, 17.6 g (0.10 mol) of benzyl methacrylate, a polymerization initiator V-601 (Wako Pure Chemical Industries, Ltd.) 2.30 g (0.01 mol) manufactured by Kogyo Co., Ltd. was dissolved in 200 g of ethylene glycol monoethyl ether acetate, and the resulting solution was purged with nitrogen in the same manner as described above.

  The temperature of the 2 L flask containing ethylene glycol monoethyl ether acetate was raised until the internal temperature reached 80 ° C., and then 2.30 g (0.01 mol) of a polymerization initiator V-601 was added and stirred for 5 minutes. . Thereafter, the monomer mixed solution was added dropwise over 6 hours with stirring. After the dropping, the mixture was further heated and stirred for 2 hours, and then the reaction solution was cooled to room temperature and dropped into 3 L of hexane to precipitate a polymer. The filtered solid was dissolved in 500 ml of acetone, dropped again into 3 L of hexane, and the filtered solid was dried under reduced pressure to obtain 151 g of 4-acetoxystyrene / t-butyl methacrylate / benzyl methacrylate copolymer.

  40.00 g of the polymer obtained above was dissolved in 200 ml of tetrahydrofuran, 5 ml of a 2.38 mass% tetramethylammonium hydroxide aqueous solution was added, and the mixture was stirred for 1 hour at room temperature. Precipitated. The precipitate was washed with distilled water and then dried under reduced pressure. After dissolving the polymer in 100 ml of ethyl acetate, 35.5 g of polymer (B-3-2) was obtained by adding hexane to the precipitated polymer as a powder by drying under reduced pressure. The weight average molecular weight by GPC was 18000, and the molecular weight dispersity (Mw / Mn) was 1.58.

Except for changing the amount of the monomer and initiator used, the resin exemplified in Table 1 was synthesized in the same manner as in Synthesis Example 1 above. Table 1 shows the composition ratio, weight average molecular weight (Mw), and molecular weight dispersity (Mw / Mn) of the resin. The composition ratio (molar ratio) corresponds to the order from the left of the repeating unit in the resin structure exemplified above. In addition, resin B-3-1, B-3-2, and B-3-3 of Table 1 are resin B-3 shown above as a resin structure, respectively, and the quantity of a polymerization initiator And the reaction conditions are appropriately changed, and the composition ratio, molecular weight, or dispersity is different.

(Preparation of resist composition)
Carboxylic acid generator (A), resin (B), acid generator (C), nitrogen-containing basic compound (D) and surfactant (E) are propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) and propylene glycol After dissolving in a mixed solvent of monomethyl ether (hereinafter abbreviated as PGME) or a single solvent to prepare a solution having a solid content concentration of 10.0% by mass, the obtained solution is subjected to microfiltration with a membrane filter having a 0.1 μm aperture. A resist solution was obtained.

Table 2 below shows the resist solutions used for the evaluation. Here, the addition amount (mass%) of each component other than a solvent means the mass% with respect to solid content except a solvent. The addition amount (mass%) of a solvent means the mass% only with a solvent.

Nitrogen-containing basic compound (D)
D-1: Dicyclohexylmethylamine D-2: Tetra- (n-butyl) ammonium hydroxide D-3:

Surfactant (E)
E-1: Fluorosurfactant, MegaFuck F-176 (Dainippon Ink Chemical Co., Ltd.)
E-2: Fluorine / silicone surfactant, MegaFac R08 (Dainippon Ink Chemical Co., Ltd.)
E-3: Silicon-based surfactant, siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Carboxylic acid generator

[Pattern preparation and evaluation 1]
The positive resist solution prepared as described above was uniformly applied on a substrate having a SiN film having a thickness of 100 nm that had been subjected to HMDS treatment at 110 ° C. for 35 seconds using a spin coater Mark8 manufactured by Tokyo Electron, Heat drying was performed at 130 ° C. for 60 seconds to form a positive resist film having a thickness of 0.25 μm. The resist film was subjected to pattern exposure under the exposure conditions of NA = 0.80 and σ = 0.80 using a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C wavelength 248 nm). After irradiation, it was baked at 130 ° C. for 60 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried. The obtained pattern was evaluated by the following method. The results are shown in Table 3.

(Heming)
The presence or absence of a resist residue in the space portion was evaluated with an exposure amount at which a 150 nm resist pattern was obtained with a mask pattern having a mask size of 150 nm and a pitch of 300 nm.
○: Resist residue is not confirmed in the space.
Δ: Resist residue is slightly confirmed in the space portion.
X: Resist residue is clearly confirmed in the space portion.

(Mask error enhancement factor (MEEF))
Slope of the change in size of the resist pattern when the mask size is changed from 140 nm to 160 nm while the pitch is fixed at 300 nm with an exposure amount at which a mask pattern with a mask size of 150 nm and a pitch of 300 nm can be obtained. Was MEEF. The closer this value is to 1, the better.

(defect)
With a mask pattern having a mask size of 150 nm and a pitch of 300 nm, a 0.15 μm pattern was exposed at 78 locations within the wafer surface with an exposure amount that would yield a 150 nm resist pattern. The number of development defects of the obtained patterned wafer was measured with KLA-2360 manufactured by KLA-Tencor Corporation. In this case, the inspection area was 205 cm ² in total, the pixel size was 0.25 μm, the threshold = 30, and the inspection light was visible light. A value obtained by dividing the obtained numerical value by the inspection area was evaluated as the number of defects (pieces / cm ² ).

[Pattern preparation and evaluation 2]
A similar evaluation was performed except that a substrate having a 31.5 nm thick SiON film was used. The results are shown in Table 4.

  From the results shown in Tables 3 and 4, it was found that the resist composition of the present invention can provide a rectangular pattern having no resist residue in the space even on a basic substrate such as SiN or SiON.

Claims (5)

(A) a compound that generates a carboxylic acid represented by the following formula (I) by irradiation with an actinic ray or radiation,
(B) an alkali-insoluble or hardly-alkali-soluble resin protected with an acid-decomposable group, which becomes alkali-soluble when the acid-decomposable group is decomposed; and (C) by irradiation with actinic rays or radiation. A positive resist composition comprising a compound that generates an acid other than the carboxylic acid represented by formula (I).

In formula (I),
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. The alkyl group, cycloalkyl group, alkenyl group and aryl group may have a substituent. R ₁ and R ₂ may be bonded to each other to form a ring. The positive resist composition according to claim 1, wherein the resin (B) contains a repeating unit represented by the following formulas (II), (III) and (IV).

In formulas (II) to (IV),
A represents a group that decomposes and leaves by the action of an acid.
R ₃ each independently represents a hydrogen atom or a methyl group.
R ₄ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms containing a halogen atom and / or an oxygen atom. Represents a phenyl group, an aralkyl group, a carbamoyl group, a cyano group, or a nitro group.
m represents 1 or 2.
n represents an integer of 0 to 2.   3. The positive resist composition according to claim 1, wherein the resin (B) has a mass average molecular weight of 15000 to 25000.   The positive resist composition according to claim 1, further comprising (D) a nitrogen-containing organic basic compound.   A pattern forming method comprising: forming a resist film using the positive resist composition according to claim 1, exposing and developing the resist film.