JP2010181729A - Actinic ray-sensitive or radiation-sensitive resin composition and method for forming pattern by using the same - Google Patents

Abstract

【選択図】なしAn actinic ray-sensitive or radiation-sensitive resin composition capable of satisfying a wide exposure latitude, reduced pattern tailing, good pattern shape, excellent dry etching resistance, and forming a pattern with few defects after development. And providing a pattern forming method using the same.
(A) A resin containing repeating units represented by formulas (I), (II) and (III), which is soluble in an alkali developer by the action of an acid, and (B) two or more types An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound capable of generating an acid upon irradiation with an actinic ray or radiation.

[Selection figure] None

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other photofabrication processes. Specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition that can be suitably used for pattern formation with high definition using KrF excimer laser light, electron beam, EUV light, and the like, and the same. The present invention relates to a pattern forming method.

  In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.

  Conventionally, in the manufacturing process of semiconductor devices such as IC and 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.

  In lithography using KrF excimer laser light, it is important to satisfy a wide exposure latitude, a wide focus latitude, a good pattern shape, and fewer defects after development. A solution is needed.

  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.

  However, since carboxylic acid is generated in the exposed area, the dissolution rate in the developer becomes too high, and when the resist pattern is actually formed on the substrate, the upper part of the pattern becomes thin, and the ideal rectangular pattern is not formed. There is. In order to solve this problem, for example, Patent Document 2 proposes a polymer having a repeating unit that reduces the solubility of the polymer in an alkali developer such as methyl methacrylate and styrene.

However, when a polymer having a repeating unit having extremely high hydrophobicity such as styrene is used for a positive resist composition, the solubility in an alkali developer is too low, and defects may easily occur. .
On the other hand, when a repeating unit having a relatively low hydrophobicity such as methyl methacrylate is used, the above development defects are unlikely to occur, but on the other hand, plasma etching resistance is insufficient and selective etching is difficult. Become.
Patent Document 3 introduces a resist composition containing a highly reactive photoacid generator.

  However, in any combination of these, it is difficult to achieve both lithographic performance, and in particular, it is not possible to satisfy the requirements of wide exposure latitude, reduced pattern tailing, good pattern shape and dry etching resistance, and few defects after development. is the current situation.

US Pat. No. 5,561,194 Japanese Patent No. 3116751 Japanese National Patent Publication No. 11-501909

  SUMMARY OF THE INVENTION An object of the present invention is to solve the problem of performance improvement technology in microfabrication of a semiconductor device using actinic rays or radiation, particularly KrF excimer laser light, electron beam or EUV light. An actinic ray-sensitive or radiation-sensitive resin composition capable of obtaining a pattern with reduced pulling, good pattern shape, excellent dry etching resistance, and having few defects after development, and a pattern forming method using the same It is to provide.

As a result of intensive studies, the present inventors have achieved the object of the present invention by the following configuration.
(1) (A) a resin containing each repeating unit represented by formulas (I), (II) and (III), which is soluble in an alkaline developer by the action of an acid, and (B) two or more types An actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with an actinic ray or radiation.

In the formula (II), R ₁ represents a hydrogen atom or a methyl group.
In the formula (III), R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. n represents an integer of 0 to 5. When n is 2 or more, the plurality of R ₂ may be the same or different.

  (2) The compound (B) contains at least two kinds of compounds that generate acids upon irradiation with actinic rays or radiation, wherein the structures of acids generated upon irradiation with actinic rays or radiation are different from each other. The actinic ray-sensitive or radiation-sensitive resin composition described.

  (3) At least one of the compounds capable of generating an acid upon irradiation with actinic rays or radiation of component (B) contains a fluorine atom in the acid generated upon irradiation with actinic rays or radiation (1) or (2) The actinic ray-sensitive or radiation-sensitive resin composition described in 1.

  (4) Any of (1) to (3), wherein the compound that generates an acid upon irradiation with an actinic ray or radiation of component (B) is independently selected from a sulfonium salt, an iodonium salt, diazodisulfone, or oxime sulfonate. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1.

  (5) The compound that generates an acid upon irradiation with actinic rays or radiation of the component (B) is independently selected from a sulfonium salt, diazodisulfone, or oxime sulfonate, according to any one of (1) to (3) An actinic ray-sensitive or radiation-sensitive resin composition.

  (6) The active light beam according to any one of (1) to (5), which contains at least two kinds of diazodisulfone and sulfonium salt as a compound that generates acid upon irradiation with active light or radiation of component (B) Or radiation sensitive resin composition.

  (7) The actinic ray-sensitive or radiation-sensitive property according to any one of (1) to (6), wherein the resin (A) has a mass average molecular weight of 15,000 to 25,000. Resin composition.

  (8) The content of the repeating units represented by the formulas (I), (II) and (III) is 55 to 75 mol%, 15%, respectively, with respect to all repeating units contained in the resin of the component (A). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (7), characterized by being -35 mol% and 5-20 mol%.

(9) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (8), further comprising (C) an organic basic compound.
(10) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (9), further comprising (D) a surfactant.
(11) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (10), further comprising a solvent.
(12) The actinic ray-sensitive or radiation-sensitive resin composition according to (11), which contains propylene glycol monomethyl ether acetate as a solvent.
(13) The actinic ray-sensitive or radiation-sensitive resin composition according to (12), further containing propylene glycol monomethyl ether as a solvent.
(14) A step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (13), and exposing and developing the film. Pattern forming method.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention satisfies a wide exposure latitude, reduced pattern tailing, a good pattern shape, and excellent dry etching resistance, and further has a pattern with few defects after development. It became possible to get.

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] Resin (A)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a repeating unit represented by formulas (I), (II) and (III), and is soluble in an alkaline developer by the action of an acid. Resin (hereinafter also referred to as “resin (A)”).

In formulas (II) and (III),
R ₁ each independently represents a hydrogen atom or a methyl group.
R ₂ represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
n represents an integer of 0 to 5. When n is 2 or more, the plurality of R ₂ may be the same or different.

  First, the repeating unit represented by the formula (I) will be described.

In the present invention, the resin (A) preferably contains at least one of the structures represented by the formula (Ia) and the formula (Ib) as the repeating unit represented by the formula (I). Both may be included. When both are included, the resin (A) may be a mixture of a resin containing the structure represented by the formula (Ia) and a resin containing the structure represented by the formula (Ib). .

The preferable composition ratio in the resin (A) of the repeating unit represented by the formula (I) is 55 to 75 mol% with respect to all the repeating units in the resin (A). The repeating unit of Ia) is 55 to 75 mol%, and the repeating unit of the formula (Ib) is 0 to 20 mol%.
It is preferable to contain the repeating unit represented by the formula (I) in the above range from the viewpoint of achieving both pattern tailing and defect performance.

Next, the repeating unit represented by the formula (II) will be described.
The repeating unit represented by the formula (II) is specifically represented by the following structure.

  In the present invention, it is particularly preferred that the resin (A) contains the structure of the formula (II-a) as the repeating unit represented by the formula (II), and the formulas (II-a) and (II-b) Both of them may be included.

The preferable composition ratio in the resin (A) of the repeating unit represented by the formula (II) is 15 to 35 mol% with respect to all the repeating units in the resin (A).
Setting the content of the repeating unit represented by the formula (II) within the above range is preferable from the viewpoint of achieving both a dissolution rate in an alkali developer and an exposure latitude.

Next, the repeating unit represented by the formula (III) will be described.
R ₂ in the repeating unit represented by the formula (III) represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and n represents an integer of 0 to 5. When n is 2 or more, the plurality of R ₂ may be the same or different. Further, from the viewpoint of the dissolution rate in an alkali developer, R ₂ is more preferably a hydrogen atom.

The alkyl group in R ₂ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. Examples thereof include a methyl group, an ethyl group, and a t-butyl group.
The cycloalkyl group in R ₂ is preferably a cycloalkyl group having 5 to 30 carbon atoms.
The in the aryl group R _2, for example, it may be mentioned a benzyl group, having 6 to 15 carbon atoms, a naphthyl group.
The aralkyl group in R ₂ is preferably one having 7 to 13 carbon atoms, and examples thereof include a methylbenzyl group, a methylphenethyl group, and a naphthylmethyl group.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group in R ₂ may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and a halogen atom.

The preferable composition ratio in the resin (A) of the repeating unit represented by the formula (III) is 5 to 20 mol% with respect to all the repeating units in the resin (A). Setting the repeating unit represented by formula (III) within the above range is preferable in order to achieve a sufficient pattern of the exposed portion while obtaining a rectangular pattern due to the dissolution inhibiting effect.
Hereinafter, although the specific structure of the repeating unit represented by Formula (III) is illustrated, it is not this limitation.

The mass average molecular weight (Mw) of the resin (A) is preferably 15,000 to 25,000. It is considered that the mobility of the actinic ray-sensitive or radiation-sensitive resin composition film is lowered by increasing the molecular weight. Therefore, when the molecular weight (Mw) is 15,000 or more, the diffusion of the generated acid can be suppressed, and various performances such as exposure latitude and standing wave are improved.
The mass average molecular weight (Mw) is preferably 25,000 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.
Here, the mass average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.
Resin (A) can synthesize | combine resin (A) with a dispersion degree of 1.0-3.0 by performing radical polymerization using a radical polymerization initiator. A resin (A) having a more preferable dispersion degree of 1.0 to 2.5 can be synthesized by living radical polymerization.
The content of the resin (A) in the composition is preferably 80 to 99 mass%, more preferably 85 to 99 mass%, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. %, And more preferably 90 to 98% by mass.
Although the specific example of resin (A) is shown below, it is not limited to these.

[2] Acid generator (B)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains two or more compounds that generate an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator (B)”). Examples of the acid generator (B) include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecoloring agent for dyes, a photochromic agent, or an actinic ray or radiation used for a micro resist. Among them, known compounds that generate an acid upon irradiation can be used, and among them, two or more kinds of structures of acids generated by irradiation with actinic rays or radiation (hereinafter referred to as “generated acid”) are different from each other. It is preferable to select and use the compound appropriately.

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 (B) Can be mentioned.

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
Z ⁻ 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. The organic group in rc ₁ to Rc _3, include those having 1 to 30 carbon atoms, preferably an optionally substituted alkyl group, an aryl group, or a plurality of these, 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 Z- in formula (ZI).
Specific examples of the compound (ZI-3) include the compounds exemplified in paragraphs 0047 and 0048 of JP-A No. 2004-233661, and paragraphs 0040 to 0046 of JP-A No. 2003-35948. it can.

Next, general formulas (ZII) and (ZIII) will be described.
In formula (ZII), (ZIII), R 204 ~R 207 each independently an optionally substituted aryl group, which may have a substituent, an alkyl group or a substituted group, The cycloalkyl group which may have is represented.
Specific examples and preferred examples of the aryl group of R _{204 to} R ₂₀₇ are the same as those described as the aryl group as R _{201 to} R ₂₀₃ in the compound (ZI-1).
Specific examples of the alkyl group and cycloalkyl group of R ₂₀₄ to R _207, examples of suitable, and those described as a linear, branched or cyclic alkyl group as R ₂₀₁ to R ₂₀₃ in the compound (ZI-2) It is the same.
Z ^- is, in the general formula (ZI) Z ^- synonymous.

Among the compounds capable of generating an acid upon irradiation with actinic rays or radiation as the acid generator (B), compounds represented by the following general formulas (ZVI), (ZVII) and (ZVIII) 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 (B), more preferred are compounds represented by the general formulas (ZI) to (ZIII), and even more preferred. Is a compound represented by (ZI), most preferably a compound represented by (ZI-1) to (ZI-3).

Of the two or more kinds of acid generators (B), at least one kind preferably contains a fluorine atom in the generated acid, more preferably a compound containing a fluorinated aryl group or a fluorinated alkyl group. . More preferably, the structure of the anion of the generated acid is a case where Rc _{1 to} Rc ₃ in the general formulas (AN1) to (AN3) are a fluorinated aryl group or a fluorinated alkyl group.

The two or more acid generators (B) are preferably selected from sulfonium salts, iodonium salts, diazodisulfones, or oxime sulfonates, and more preferably acid generators having three or more different carbon atoms in the generated acid. The combination is preferable from the viewpoint of a good profile.
Examples of the sulfonium salt include the compound represented by the general formula (ZI). Examples of the iodonium salt include the compound represented by the general formula (ZII). Examples of the diazodisulfone include The compound represented by general formula (ZIII) can be mentioned, As an oxime sulfonate, the compound represented by the said general formula (ZVI) can be mentioned.

  The combination of two or more acid generators (B) is more preferably selected from sulfonium salts, diazodisulfones, or oxime sulfonates, and most preferably includes at least two types of diazodisulfones and sulfonium salts. It is a combination.

  The content of the acid generator (B) in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 0.5%, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is 10 mass%, More preferably, it is 1-7 mass%.

Specific examples of the acid generator (B) are shown below, but are not limited thereto.

[3] Organic basic compound (C)
The actinic ray-sensitive or radiation-sensitive resin 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. Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and paragraph [0066] of US2007 / 0224539A1. And compounds (C1-1) to (C3-3) exemplified in the above.

  Preferred organic basic compounds include guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and the like. . 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 organic basic compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenyl. Imidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine 4-aminoethylpyridine, 3-aminopi Lysine, 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 Examples include, but are not limited to, pyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine. Is not to be done.

  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 ratio of the compound (B) that generates an acid upon irradiation with actinic rays or radiation and the organic basic compound (C) in the composition is organic basic compound / acid generator (molar ratio) = 0.01-10. It is preferable that That is, the molar ratio is preferably 10 or less from the viewpoint of sensitivity and resolution, and is preferably 0.01 or more from the viewpoint of suppressing the reduction in resolution due to the pattern thickening over time until post-exposure heat treatment. The organic basic compound / acid generator (molar ratio) is more preferably 0.05 to 5, and still more preferably 0.1 to 3.

[4] Surfactant (D)
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 compounding 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.

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 actinic ray-sensitive or radiation-sensitive resin composition.

[5] Solvent The actinic ray-sensitive or radiation-sensitive resin 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 the composition 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, anisole, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol mono Ethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable. Et solvents may be used alone or in combination with.

  In the present invention, a solvent containing propylene glycol monomethyl ether acetate is preferable, and a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether is more preferable.

[6] Other additives The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a photobase generator, 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. -194434, 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. Carboxylic acid generator (E)
You may use the compound (henceforth a compound (E) or a carboxylic acid generator) which generate | occur | produces carboxylic acid by irradiation of actinic light or a radiation.
As the carboxylic acid generator, a compound represented by the following general formula (E) is preferable.

In general formula (E), R _{21 to} R ₂₃ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. 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.

In the general formula (E), 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.
Examples of the substituent that the alkyl group, cycloalkyl group or alkenyl group may have include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), an aryl group (a phenyl group, a naphthyl group, etc.), a hydroxy group, An alkoxy group (methoxy group, ethoxy group, butoxy group, etc.) 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.) and the like.

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.
R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.

Examples of the substituent that the alkyl group, cycloalkyl group, and alkenyl group may have are the same as those described as examples of the substituent when R ₂₁ is an alkyl group. Examples of the substituent for the aryl group, the R ₂₁ may be the same as those mentioned as examples of the substituent when it is an aryl group.

R ₂₄ is preferably a hydrogen 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, an aryl group having 6 to 24 carbon atoms, and more Preferably, they are a C1-C18 alkyl group, a C3-C18 cycloalkyl group, and a C6-C18 aryl group, Most preferably, a C1-C12 alkyl group, C3-C3 A cycloalkyl group having 12 carbon atoms and 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.

  Two or more of the cation moieties of formula (E) 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 formula (E). May be.

Although the preferable specific example of the compound (E) 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 compound (E) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 0 to 10% by mass, more preferably 0 to 5%, based on the total solid content of the composition. % By mass, particularly preferably 0 to 3% by mass. In addition, these compounds that generate a carboxylic acid upon irradiation with actinic rays or radiation may be used alone or in combination of two or more.

3. Antioxidant The actinic ray-sensitive or radiation-sensitive resin composition of the present invention can 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.

  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, and more preferably 10 ppm or more with respect to the total solid mass in the actinic ray-sensitive or radiation-sensitive resin composition. Is 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.

[7] Film Formation The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is applied onto a substrate to form a thin film. The thickness of this coating film is preferably 0.05 to 4.0 μm.

  An antireflection film may be provided under the actinic ray-sensitive or radiation-sensitive resin composition film. 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.
If necessary, an antireflection film can be used as an upper layer of the actinic ray-sensitive or radiation-sensitive resin composition film.
Examples of the antireflection film include AQUATAR-II, AQUATAR-III, AQUATAR-VII, and AQUATAR-VIII manufactured by AZ Electronic Materials.

  In the manufacture of precision integrated circuit elements, the pattern forming process on the resist film is carried out on the substrate (eg, silicon / silicon dioxide coated substrate, glass substrate, ITO substrate, quartz / chromium oxide coated substrate, etc.). A resist pattern is formed by applying a resist composition, forming a resist film, and then irradiating actinic rays or radiation such as KrF excimer laser light, electron beam, EUV light, etc., heating, developing, rinsing and drying. Can be formed.

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 ((A-1) -1) 600 g of ethylene glycol monoethyl ether acetate was placed in a 2 L flask and purged with nitrogen 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 a 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 (A-1) was obtained by adding hexane to the precipitated polymer as a powder by drying under reduced pressure. The mass average molecular weight by GPC was 14,000, and the molecular weight dispersity (Mw / Mn) was 1.50.

Except changing the monomer to be used, the resin whose structure was previously illustrated in Table 1 was synthesized in the same manner as in Synthesis Example 1 above. Table 1 shows the resin composition ratio, mass average molecular weight (Mw), and molecular weight dispersity (Mw / Mn). The structures of the resins (A-1) -1 and (A-1) -2 are both A-1, and each has a different composition ratio, molecular weight, and degree of dispersion.

(Preparation of resist composition)
Resin, acid generator, organic basic compound and surfactant are dissolved in a mixed solvent or a single solvent of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) and propylene glycol monomethyl ether (hereinafter abbreviated as PGMEA) to obtain a solid content. After preparing a solution having a concentration of 10.0% by mass, the obtained solution was microfiltered with a membrane filter having a 0.1 μm aperture to obtain a resist solution.

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. About a solvent, the mixing ratio (mass%) of PGMEA and PGME is shown.

(Organic basic compounds)
C-1: Dicyclohexylmethylamine C-2: 2,4,6-triphenylimidazole C-3: Tetra- (n-butyl) ammonium hydroxide C-4:

(Surfactant)
D-1: Fluorosurfactant, MegaFuck F-176 (manufactured by Dainippon Ink & Chemicals, Inc.)
D-2: Fluorine / silicone surfactant, MegaFac R08 (manufactured by Dainippon Ink & Chemicals, Inc.)
D-3: Silicon-based surfactant, siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
[Pattern preparation and evaluation 1 (KrF)]
The positive resist solution prepared as described above is uniformly applied onto a substrate coated with a 60 nm antireflection film (Drew 42 from Brewer Science) using a spin coater Mark8 manufactured by Tokyo Electron, and heated at 130 ° C. for 60 seconds. Drying was performed to form a positive resist film having a thickness of 0.4 μm. The resist film was subjected to pattern exposure under the exposure conditions of NA = 0.68 and σ = 0.60 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.

(Exposure latitude (EL))
About the resist pattern obtained by carrying out similarly to the above, the amount of exposure by which a line width is observed with a scanning electron microscope (S-8840 made by Hitachi, Ltd.), and a resist pattern of 150 nm is obtained with a mask pattern having a mask size of 150 nm and a pitch of 300 nm. Was the effective sensitivity, and the value (percentage) obtained by dividing the exposure amount at which the line width changed by 10% by the effective exposure amount was defined as EL.

(Profile)
The cross-sectional shape of the resist pattern with a width of 150 nm was observed with a cross-sectional SEM, and the side surface was cut almost vertically and the effect of standing waves was suppressed, and among them, the better one was 2A, which was slightly tapered. Although a standing wave effect is suppressed, B is used, and a side surface is wavy and a standing wave effect appears.

(Heming)
In the above effective sensitivity, a pattern having a mask size of 0.15 μm was observed with a scanning electron microscope (S-8840 manufactured by Hitachi, Ltd.), and the line width between the upper surface (X) of the pattern and the substrate interface (Y) was observed. 1/2 ((Y-X) / 2) was used as an index for tailing.

(Residual film rate (plasma etching resistance))
After forming a 0.4 μm-thick positive resist film on the hexamethyldisilazane-treated wafer, a mixed gas of CF ₄ (10 mL / min), O ₂ (20 mL / min), Ar (1000 mL / min) Was used and plasma etching was performed for 30 seconds at a temperature of 23 ° C. Thereafter, the residual film amount of the resist film was measured, and the value obtained by dividing the resist film by the original film thickness of 0.4 μm and multiplying by 100 was defined as the residual film ratio (%). The larger the remaining film ratio, the better the plasma etching resistance.

[Pattern preparation and evaluation 2 (EB)]
The same resist solution as that used in pattern preparation and evaluation 1 (KrF) except that the solid content concentration was changed to 8% by mass was applied to a hexamethyldisilazane-treated silicon wafer using a spin coater Mark8 manufactured by Tokyo Electron. And then baked at 120 ° C. for 60 seconds to obtain a film having an average film thickness of 0.3 μm.

  The resist film was irradiated with an electron beam using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). After irradiation, it was baked at 130 ° C. for 60 seconds, developed with 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 4.

(Resolution)
The line width of the obtained pattern was observed with a scanning electron microscope (S-9260, manufactured by Hitachi, Ltd.), and the irradiation energy when resolving a 0.15 μm line (line: space = 1: 1) was defined as sensitivity. The scanning electron microscope was used to observe how many μm the line: space = 1: 1 pattern was resolved with the irradiation energy indicating this sensitivity.

(defect)
The irradiation energy indicating the sensitivity obtained above is used to perform electron beam irradiation, baking and development in the same manner as described above, thereby patterning a line: space = 1: 1, 0.15 μm line, 3 μm wide, 3 μm long The number of development defects (pieces / cm ² ) was observed at 100 locations by the scanning electron microscope.

(Residual film rate)
Evaluation was performed in the same manner as in Evaluation 1 (KrF).

[Pattern preparation and evaluation 3 (EUV)]
The same resist solution used in pattern preparation and evaluation (KrF1) except that the solid content concentration was changed to 6% by mass was applied onto a silicon wafer subjected to hexamethyldisilazane treatment using a spin coater Mark8 manufactured by Tokyo Electron. The film was baked at 120 ° C. for 60 seconds to obtain a film having an average film thickness of 0.15 μm.

  The obtained resist film is exposed using EUV light (wavelength 13 nm: EUVES, manufactured by litho-track Japan Co., Ltd.) while changing the exposure amount by 0.5 mJ in the range of 0 to 20.0 mJ. Baked for a second. Then, using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate at each exposure amount was measured to obtain a dissolution rate curve.

(Resolution (dissolution contrast))
In this dissolution rate curve, the exposure amount when the dissolution rate of the resist is saturated was taken as sensitivity, and the dissolution contrast (γ value) was calculated from the gradient of the linear portion of the dissolution rate curve as an index of resolution. The larger the γ value, the better the dissolution contrast and the higher the resolution. The results are shown in Table 5.

(Development defects)
Exposure by the exposure amount indicating the sensitivity, baking and development similar to the above, and the boundary between the exposed portion and the unexposed portion is 3 μm wide and 100 μm in length of 3 μm. The number of development defects ( Pieces / cm ² ). The results are shown in Table 5.

(Residual film rate)
Evaluation was performed in the same manner as in Evaluation 1 (KrF). The results are shown in Table 5.

  From the results shown in Table 3, Table 4 and Table 5, according to the resist composition of the present invention, in the fine processing using KrF excimer laser light, electron beam or EUV light, the tailing is reduced and wide. It was found that the exposure latitude, good pattern shape, and excellent dry etching resistance were satisfied, and a pattern with few defects after development could be provided.

Claims (9)

(A) a resin containing each repeating unit represented by formulas (I), (II) and (III), which is soluble in an alkaline developer by the action of an acid, and (B) two or more types of activities An actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with light or radiation.

In the formula (II), R ₁ represents a hydrogen atom or a methyl group.
In the formula (III), R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. n represents an integer of 0 to 5. When n is 2 or more, the plurality of R ₂ may be the same or different.   2. The sensation according to claim 1, wherein the compound that generates an acid upon irradiation with an actinic ray or radiation of the component (B) contains at least two compounds having different structures of acids generated upon irradiation with an actinic ray or radiation. An actinic ray-sensitive or radiation-sensitive resin composition.   The activity-sensitive composition according to claim 1 or 2, wherein at least one of the compounds capable of generating an acid upon irradiation with actinic rays or radiation of component (B) contains a fluorine atom in the acid generated upon irradiation with actinic rays or radiation. A light-sensitive or radiation-sensitive resin composition.   The sensitization according to any one of claims 1 to 3, wherein the compound capable of generating an acid upon irradiation with an actinic ray or radiation of component (B) is independently selected from a sulfonium salt, an iodonium salt, diazodisulfone or oxime sulfonate. An actinic ray-sensitive or radiation-sensitive resin composition.   The actinic ray-sensitive property according to any one of claims 1 to 3, wherein the compound that generates an acid upon irradiation with actinic rays or radiation of component (B) is independently selected from sulfonium salts, diazodisulfones, or oxime sulfonates. Or a radiation sensitive resin composition.   The actinic ray-sensitive or radiation-sensitive property according to any one of claims 1 to 5, comprising at least two kinds of diazodisulfone and a sulfonium salt as compounds that generate an acid upon irradiation with actinic rays or radiation of component (B). Resin composition.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein the resin (A) has a mass average molecular weight of 15,000 to 25,000.   The content of the repeating units represented by the formulas (I), (II) and (III) is 55 to 75 mol%, 15 to 35 mol, respectively, with respect to all the repeating units contained in the resin of the component (A). The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the composition is% or 5 to 20 mol%.   A pattern forming method comprising: forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, and exposing and developing the film.