JP2013178370A - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film and pattern formation method using said composition, and electronic device manufacturing method and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an actinic ray-sensitive or radiation-sensitive resin composition improved in CDU and roundness and suited even for a liquid immersion process with a line width of 45 nm or less; an actinic ray-sensitive or radiation-sensitive film and a pattern formation method which use the composition; and an electronic device manufacturing method and an electronic device.SOLUTION: An actinic ray-sensitive or radiation-sensitive resin composition contains a compound (A) represented by the specified general formula (1), and a resin (B) whose solubility in an alkaline developer is increased by the action of an acid. (The meaning of each symbol in the general formula (1) is described in the claims.)

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as IC, circuit boards such as liquid crystals and thermal heads, and other photofabrication processes, and the composition. The present invention relates to a pattern forming method. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitable for the case of using an ultraviolet ray of 250 nm or less, an electron beam, or the like as an irradiation source, and an actinic ray-sensitive or sensitization using the composition. The present invention relates to a radiation film, a pattern formation method, an electronic device manufacturing method, and an electronic device.

The chemically amplified resist composition generates an acid in the exposed area by irradiation with radiation such as far ultraviolet light, and the acid-catalyzed reaction changes the solubility of the active radiation irradiated area and non-irradiated area in the developer. And a pattern forming material for forming a pattern on the substrate.
When a KrF excimer laser is used as an exposure light source, a resin having a basic skeleton of poly (hydroxystyrene) having a small absorption mainly in the 248 nm region is used as a main component. This is a better system than the conventional naphthoquinonediazide / novolak resin system.

On the other hand, when a further short wavelength light source, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the above chemical amplification system is not sufficient because an aromatic compound essentially shows a large absorption in the 193 nm region. It was.
For this reason, various ArF excimer laser resists containing an alicyclic hydrocarbon structure have been developed. Further, as a technique for further increasing the resolving power, development of a so-called immersion method in which the space between the projection lens and the sample is filled with a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) has been progressing. However, from the viewpoint of overall performance as a resist, it is actually difficult to find an appropriate combination of resins, photoacid generators, additives, solvents and the like to be used.

  Under such circumstances, for example, Patent Documents 1 and 2 disclose the time from exposure to post-exposure bake (PEB) by using a specific compound that decomposes upon irradiation with actinic rays or radiation. It describes that problems such as a change in pattern line width related to the length and distortion of the pattern shape (post exposure delay; PED) are suppressed, and that the pattern shape or line edge roughness is improved.

  However, in the generation of forming the latest hole pattern with a line width of 45 nm or less to which the immersion process is applied, the above prior art is not always sufficient, and the roundness in the contact hole pattern and the line width in the wafer plane are uniform. Further improvements are required in performance such as critical dimension uniformity (CDU).

JP 2006-330098 A Japanese Patent Laid-Open No. 7-333851

  In view of the above problems in the background art, the present invention uses an actinic ray-sensitive or radiation-sensitive resin composition that has improved CDU and roundness and is suitable for an immersion process with a line width of 45 nm or less, and the same. It is an object of the present invention to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, an electronic device manufacturing method, and an electronic device.

The above object is achieved by the following means.
That is, this invention has the following structures, for example.

[1] Actinic ray-sensitive or radiation-sensitive resin composition containing a compound (A) represented by the following general formula (1) and a resin (B) whose solubility in an alkali developer is increased by the action of an acid object.

In general formula (1),
R ₁ and R ₂ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. However, at least one of R ₁ and R ₂ is an aryl group, and R ₁ and R ₂ may be connected to each other to form a condensed ring.
R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R ₃ and R ₄ may be connected to each other to form a ring.
R ₅ represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group or an aralkyl group. R ₅ may be bonded to R ₃ or R ₄ to form a ring.

Q ⁻ represents —W ₁ N ⁻ W ₂ R _f or —SO ₃ ⁻ . Here, R _f represents an alkyl group, a cycloalkyl group, or an aryl group, and W ₁ and W ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or —N (R _x ) R _y —. Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x is may form a ring with R _y, may form a ring with R _N.
R _N represents an organic group containing at least one basic nitrogen atom.

[2] Q in the general formula (1) ^- is _-W 1 ^-N - a _-W 2 -R _f, sensitive or radiation-sensitive resin composition according to [1].

[3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein R ₅ in the general formula (1) is an alkoxy group.

[4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein R ₁ and R ₂ in the general formula (1) are both aryl groups.

  [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], further comprising a hydrophobic resin (HR).

  [6] The actinic ray-sensitive or radiation-sensitive resin composition according to [5], wherein the hydrophobic resin (HR) is a hydrophobic resin having at least one of a fluorine atom and a silicon atom.

  [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the resin (B) contains a repeating unit having a lactone structure or a sultone structure.

  [8] Further, it contains a compound (C) that generates an acid upon irradiation with actinic rays or radiation, and the structure of the cation moiety of the compound (C) is the same as the structure of the cation moiety of the compound (A). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7].

  [9] The actinic ray-sensitive or radiation-sensitive resin composition according to [8], wherein the content of the compound (C) is 0.1 to 30% by mass based on the total solid content of the composition.

  [10] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9].

[11] A pattern forming method comprising a step of exposing the actinic ray-sensitive or radiation-sensitive film according to [10], and a step of developing the exposed actinic ray-sensitive or radiation-sensitive film.
[12] The pattern forming method according to [11], wherein the exposure is immersion exposure.

[13] A method for manufacturing an electronic device, comprising the pattern forming method according to [11] or [12].
[14] An electronic device manufactured by the method for manufacturing an electronic device according to [13].

  ADVANTAGE OF THE INVENTION According to this invention, CDU and roundness are improved, the actinic-ray-sensitive or radiation-sensitive resin composition which can be used suitably also for the immersion process with a line | wire width of 45 nm or less, actinic light using the said composition A radiation-sensitive or radiation-sensitive film and a pattern forming method, an electronic device manufacturing method, and an electronic device are provided.

Hereinafter, 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).

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

  In addition, “exposure” in the present specification is represented not only by exposure to deep ultraviolet rays, X-rays, EUV light and the like, but also by particle beams such as electron beams and ion beams, unless otherwise specified, such as mercury lamps and excimer lasers. Drawing is also included in the exposure.

[1] Compound (A)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a compound represented by the following general formula (1) (hereinafter also referred to as “compound (A)”).

In general formula (1),
R ₁ and R ₂ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. However, at least one of R ₁ and R ₂ is an aryl group, and R ₁ and R ₂ may be connected to each other to form a condensed ring.
R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R ₃ and R ₄ may be connected to each other to form a ring.
R ₅ represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group or an aralkyl group. R ₅ may be bonded to R ₃ or R ₄ to form a ring.

Q ⁻ represents —W ₁ N ⁻ W ₂ R _f or —SO ₃ ⁻ . Here, R _f represents an alkyl group, a cycloalkyl group, or an aryl group, and W ₁ and W ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or —N (R _x ) R _y —. Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x is may form a ring with R _y, may form a ring with R _N.
R _N represents an organic group containing at least one basic nitrogen atom.

Compound (A) can be decomposed by irradiation with actinic rays or radiation, generates an HQ-A- (X) a compound represented by _{n-B-R N.} As will be described later, this compound is a compound in which the basicity is lowered, disappeared, or changed from basic to acidic as compared with the compound (A) by having an acidic group together with the basic group.
Hereinafter, the general formula (1) will be described in detail.

First, the anion part represented by the following general formula (1-1) will be described in detail.

In General Formula (1-1), Q ⁻ represents —W ₁ N ^— W ₂ R _f or —SO ₃ ^— as described above, and R _f represents an alkyl group, a cycloalkyl group, or an aryl group. W ₁ and W ₂ each independently represent —SO ₂ — or —CO—.

W ₁ and W _2, at least one of -SO ₂ - is preferably, both -SO ₂ - and particularly preferably.
The alkyl group, cycloalkyl group and aryl group as R _f each may have a substituent, preferably an alkyl group which may have a fluorine atom having 1 to 6 carbon atoms, more preferably. Is a C1-C6 perfluoroalkyl group, More preferably, it is a C1-C3 perfluoroalkyl group.
The divalent linking group in A is preferably a divalent linking group having 2 to 12 carbon atoms, for example, an alkylene group which may have a substituent, or phenylene which may have a substituent. Groups and the like. More preferably, it is an alkylene group having at least one fluorine atom, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

B represents a single bond, an oxygen atom, or —N (R _x ) R _y —, as described above, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. Represents a group. R _x is may form a ring with R _y, may form a ring with R _N.

B is -N _(R x) R _y - when referring to, the monovalent organic group represented by _{R x,} and preferably from 1 to 30 carbon atoms, e.g., alkyl group, cycloalkyl group, aryl group, aralkyl group And alkenyl groups. These groups may further have a substituent.

The alkyl group in R _x may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. It may be.

  In addition, examples of the alkyl group having a substituent include groups in which a cycloalkyl group is substituted on a linear or branched alkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). .

The cycloalkyl group in R _x may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring.

The aryl group for R _x may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.

The aralkyl group in R _x may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms.

The alkenyl group for R _x may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group exemplified as R _x .

B is -N _(R x) R _y - when referring to, the divalent organic group represented by _{R y,} preferably includes an alkylene group. In this case, examples of the ring structure that R _x and R _y may be bonded to each other include a 5- to 8-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring.

B is -N _(R x) R _y - when referring to, it is preferable that the _{R N} and _{R x} are bonded to each other to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.

  Examples of the monocyclic structure include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures. Each of the monocyclic structure and the polycyclic structure may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, and a cycloalkyl group (preferably Has 3 to 10 carbon atoms, an aryl group (preferably 6 to 14 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 15 carbon atoms), an acyloxy group (preferably carbon). And preferably an alkoxycarbonyl group (preferably 2 to 15 carbon atoms), an aminoacyl group (preferably 2 to 20 carbon atoms), and the like. Regarding the cyclic structure in the aryl group, cycloalkyl group and the like as a substituent, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15). Moreover, about the aminoacyl group as a substituent, an alkyl group (preferably C1-C15) can be mentioned as a substituent further.

R _N is, as described above, represents an organic group containing at least one basic nitrogen atom. Here, “basic nitrogen atom” means a nitrogen atom such that the pKa of the conjugate acid of the corresponding nitrogen atom is −3 or more. This pKa is preferably in the range of -3 to 15, and more preferably in the range of 0 to 15. This pKa means a calculated value obtained by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).

Represented by R _N, as the organic group containing a basic nitrogen atom, a structure having a primary to tertiary amino group, or a nitrogen-containing heterocyclic structure is more preferable. In these structures, it is preferable from the viewpoint of improving basicity that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly connected to the nitrogen atom.

The organic groups represented by R _N may further have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably 3 to 10 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxy group. Group (preferably 1 to 10 carbon atoms), acyl group (preferably 2 to 20 carbon atoms), acyloxy group (preferably 2 to 10 carbon atoms), alkoxycarbonyl group (preferably 2 to 20 carbon atoms), aminoacyl group (Preferably having 2 to 20 carbon atoms). About the cyclic structure in an aryl group, a cycloalkyl group, etc., and an aminoacyl group, you may have an alkyl group (preferably C1-C20) as a substituent further.

As the compound (1-1), a compound represented by the following general formula (4) is particularly preferable.

In the general formula (4), A, X, n, B, R N, Rf, W 1 and _{W 2} have the same meanings as those in general formula (1-1).
Specific examples of the anion structure represented by the general formula (1-1) are shown below.

The following cation structure portion in the compound (A) represented by the general formula (1) will be described in detail below.

R ₁ and R ₂ are as described above, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, where at least one aryl group of R ₁ and R _2. R ₁ and R ₂ may be connected to each other to form a condensed ring.

The alkyl group represented by R ₁ and R ₂ is, for example, preferably an alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec. -Butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl Group, eicosyl group and the like.

Examples of the cycloalkyl group represented by R ₁ and R ₂ include preferably a cycloalkyl group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like. Can do.

Examples of the alkenyl group represented by R ₁ and R ₂ include preferably 2 to 30 alkenyl groups, such as vinyl group, allyl group, and styryl group.
As the aryl group represented by R ₁ and R ₂ , for example, an aryl group having 6 to 20 carbon atoms is preferable. Specifically, a phenyl group, a naphthyl group, an azulenyl group, an acenaphthylenyl group, a phenanthrenyl group, a penalenyl group, a phenyl group, Examples thereof include a nantracenyl group, a fluorenyl group, an anthracenyl group, a pyrenyl group, and a benzopyrenyl group. Preferred are a phenyl group and a naphthyl group, and more preferred is a phenyl group.

As described above, it is preferable that at least one of R ₁ and R ₂ is an aryl group, and both R ₁ and R ₂ are aryl groups. Compared to the monoaryl type, the diaryl type has a large absorption (ε) with respect to 193 nm, and the amount of acid generated during exposure increases accordingly. As a result, CDU performance is improved because deprotection can be efficiently performed with more acid.

The aryl group as R ₁ and R ₂ may have a substituent, and the position and number where the substituent can be introduced are not particularly limited. Examples of the substituent that can be introduced include a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group or a cycloalkyl group (preferably a straight chain having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, Branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1 -Norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-buten-1-yl), an aryl group ( Preferably it is an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms. , Phenyl, naphthyl), a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, Trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Alkoxy groups such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, A butoxy, dodecyloxy, cycloalkyloxy group, for example, cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6-48 carbon atoms, more preferably 6-24 carbon atoms, for example, phenoxy 1-naphthoxy), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy and 2-tetrahydropyranyl Oxy),
Silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy group (preferably having 2 carbon atoms) 48, more preferably an acyloxy group having 2 to 24 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably 2 to 2 carbon atoms). 24 alkoxycarbonyloxy groups such as ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy groups such as cyclohexyloxycarbonyloxy, aryloxycarbonyloxy groups (preferably Is an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 1 carbon atoms). 24 carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy groups (preferably having a carbon number) 1 to 32, more preferably a sulfamoyloxy group having 1 to 24 carbon atoms, such as N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably having a carbon number) 1 to 38, more preferably 1 to 24 carbon In Niruokishi group, e.g., methylsulfonyloxy, hexadecyl sulfonyloxy, cyclohexyl sulfonyloxy)
An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably having 1 to 48 carbon atoms, more preferably carbon An acyl group having 1 to 24, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably an alkoxy having 2 to 24 carbon atoms) Examples of carbonyl groups include methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), and aryloxycarbonyl groups (preferably having 7 to 32 carbon atoms). , Yo Preferably, it is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl, and a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably a carbamoyl group having 1 to 24 carbon atoms, such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino group (Preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino),
Anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms such as anilino and N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms). A heterocyclic amino group such as 4-pyridylamino), a carbonamido group (preferably having a carbon number of 2 to 48, more preferably 2 to 24, such as acetamide, benzamide, tetradecanamide, pivaloylamide, cyclohexane Amide), ureido groups (preferably ureido groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), imide groups (preferably carbon An imide group having 36 or less, more preferably 24 or less carbon atoms, for example, N-succi Imide, N-phthalimide), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino , Octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), sulfone An amide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfone; Amide, cyclohexanesulfonamido), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N -Ethyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, phenylazo, 3-pyrazolylazo),
An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 48 carbon atoms, more preferably An arylthio group having 6 to 24 carbon atoms, such as phenylthio, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as 2-benzothiazoli Ruthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl group), an arylsulfinyl group ( Preferably it has 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms. An arylsulfonyl group (for example, phenylsulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, Isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl, N, N-dipropylsulfa , N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably carbon A phosphonyl group having 1 to 24 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having 1 to 32 carbon atoms, more preferably phosphino having 1 to 24 carbon atoms) Ilylamino group includes, for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).

As the substituent which the aryl group as R ₁ and R ₂ may have, a linear or branched alkyl group or a cycloalkyl group (for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl) is preferable. , Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), hydroxyl group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably An alkoxy group having 1 to 24 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups, for example, cyclopentyloxy, cyclohexyloxy), amino Group (preferably carbon 32 or less, more preferably an amino group having 24 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), an alkoxycarbonylamino group (preferably An alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, and cyclohexyloxycarbonylamino). .

As the substituent that the aryl group as R ₁ and R ₂ may have, a linear or branched alkyl group or a cycloalkyl group (for example, methyl, ethyl, propyl, isopropyl, butyl, t- Butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), hydroxyl group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably Is an alkoxy group having 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups, such as cyclopentyloxy, cyclohexyloxy), Alkoxycarbonyl Mino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonyl Amino).

As the substituent that the aryl group as R ₁ and R ₂ may have, a linear or branched alkyl group or a cycloalkyl group (for example, methyl, ethyl, propyl, isopropyl, butyl, t- Butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkoxy group (preferably having 1 to 48 carbon atoms, more preferably having 1 to 48 carbon atoms) Examples thereof include 1 to 24 alkoxy groups such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy and cycloalkyloxy groups such as cyclopentyloxy and cyclohexyloxy.

As described above, R ₁ and R ₂ may be linked, and are preferably linked via, for example, a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted alkylene group, —O—, —S—, —CO—, —N (R) — (wherein R is a hydrogen atom, an alkyl group, an alkylcarbonyl group). Group or an alkyloxycarbonyl group), or a divalent linking group in which a plurality of these are combined.

R ₃ and R ₄ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, as described above. These groups may have a substituent. R ₃ and R ₄ may be linked.

The alkyl group as R ₃ and R ₄ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And a branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group. Examples of the alkyl group having a substituent include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, and an ethoxycarbonylmethyl group.

Further, the cycloalkyl group as R ₃ and R ₄ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.

The aryl group as R ₃ and R ₄ is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The alkenyl group as R ₃ and R ₄ is preferably an alkenyl group having 2 to 20 carbon atoms. Specifically, the alkenyl group has a double bond at any position of the alkyl group as R ₃ and R ₄ described above. Groups.

Examples of the substituent that these groups may have include specific examples similar to the substituents that the aryl group as R ₁ and R ₂ described above may have.

The ring structure that R ₃ and R ₄ can form together is preferably a 5-membered or 6-membered ring, particularly preferably a 6-membered ring.

R ₃ or R ₄ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ₃ and R ₄ may be linked.
More preferably, they are a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ₃ and R ₄ may be linked.
More preferably, they are a hydrogen atom and an alkyl group, and R ₃ and R ₄ may be linked.

R ₅ represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group, or an aralkyl group as described above. These groups may have a substituent. R ₅ may be linked to R ₃ or R ₄ to form a ring.

Specific examples of the alkyl group, cycloalkyl group, alkenyl group, and aryl group represented by R ₅ include the same examples as the alkyl group, cycloalkyl group, alkenyl group, and aryl group as R ₃ and R ₄ described above. The same applies to the substituent that these groups may have.

As an aralkyl group represented by R ₅ , for example, an aralkyl group having 7 to 20 carbon atoms is preferable, and specific examples include a benzyl group and a phenethyl group. Examples of the substituent that the aralkyl group may have include specific examples similar to the substituents that the aryl group as R ₁ and R ₂ described above may have.

In the alkoxy group represented by R ₅ , the alkyl moiety in the alkoxy group may be linear, branched or cyclic. The alkoxy group preferably has 1 to 10 carbon atoms, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group. N-pentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, cycloheptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n -Nonyloxy group, n-decyloxy group, etc. can be mentioned. Of these alkoxy groups, a methoxy group, an ethoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and the like are preferable.

In the alkoxy group represented by R ₅ , the alkyl moiety in the alkoxy group may include a group capable of leaving by the action of an acid, such as a tertiary alkyl group such as a t-butyl group. Good. Examples of the group capable of leaving by the action of an acid include —C (R ₁₁ ) (R ₁₂ ) (R ₁₃ ), —C (R ₁₁ ) (R ₁₂ ) (OR ₁₄ ), —C (R _a ) ( And a group represented by R _b ) (OR ₁₄ ). Here, R < ₁₁ > -R < ₁₄ > represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group each independently. R ₁₁ and R ₁₂ may be bonded to each other to form a ring. R _a and R _b each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Of the alkoxy groups eliminated by the action of these acids, t-butoxy groups, t-amyloxy groups, and the like are preferable.

In one embodiment of the present invention, R ₅ is preferably an alkyl group, a cycloalkyl group, or an alkoxy group, and more preferably an alkoxy group. Note that the carbon atom bonded to the oxygen atom may be any of primary carbon, secondary carbon, and tertiary carbon.

As described above, R ₅ may be linked to R ₃ or R _4, and for example, it is preferable to form a 5- to 7-membered lactone structure by linkage. In addition, other ring structures may be condensed so as to form a bicyclo structure or a spiro structure in the lactone structure.

Below, the preferable specific example of the cation structure of the compound (A) represented by General formula (1) is shown.

Hereinafter, although the specific example of the compound (A) in this invention is shown, it is not limited to these.

In the composition of this invention, a compound (A) can be used individually by 1 type or in combination of 2 or more types.
The content of the compound (A) in the composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 9% by mass, and 1 to 8% by mass based on the total solid content in the composition. Is particularly preferred.

  Compound (A) may be a commercially available product or may be synthesized by a known method.

Next, the compound (A) of the present invention and other components will be described.
As described above, the compound (A) decomposes upon exposure to actinic rays or radiation to generate an acid in the exposed portion, but is neutralized by capturing a proton of the acid by a basic group present in the molecule. In the exposed portion, the compound (A) does not substantially generate an acid (does not contribute to the chemical amplification action). In addition, since the basicity (proton capturing ability) of the compound (A) is reduced or disappears in the exposed area, the acid decomposition reaction is performed as compared with the case of using a basic compound having no such function. Acid is not trapped. As a result, the intended reaction between the acid and the resin can proceed more reliably in the exposed area. Therefore, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a chemically amplified resist composition containing an acid generator (C) in terms of sensitivity. The composition of the present invention is preferably a positive resist composition containing a resin (B) whose solubility in an alkaline developer is increased by the action of an acid.

[2] Resin (B) whose solubility in an alkaline developer is increased by the action of an acid
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin whose solubility in an alkaline developer is increased by the action of an acid (hereinafter also referred to as “acid-decomposable resin” or “resin (B)”). Containing.

The acid-decomposable resin is a group capable of decomposing under the action of an acid into an alkali-soluble group (hereinafter also referred to as “acid-decomposable group”) on the main chain or side chain of the resin, or both of the main chain and side chain. Have
The resin (B) is preferably insoluble or hardly soluble in an alkali developer.

The acid-decomposable group preferably has a structure protected with a group capable of decomposing and leaving an alkali-soluble group by the action of an acid.
Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. 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, etc. Is mentioned.

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

A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these alkali-soluble groups is substituted with a group capable of leaving with an acid.
As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - 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 repeating unit having an acid-decomposable group that can be contained in the resin (B) is preferably a repeating unit represented by the following general formula (AI).

In general formula (AI),
Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxy group or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group. Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.
Examples of the alkyl group rx ₁ to Rx _3, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, those having 1 to 4 carbon atoms such as t- butyl group.

Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, A polycyclic cycloalkyl group such as an adamantyl group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group is preferable.

  Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, An alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.

  The total content of repeating units having an acid-decomposable group is preferably from 20 to 70 mol%, more preferably from 30 to 50 mol%, based on all repeating units in the resin.

  Although the preferable specific example of the repeating unit which has an acid-decomposable group is shown below, this invention is not limited to this.

In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of Z, the plurality of Z may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of R ₁₀ in formula (II-1) described later.

The resin (B) is a resin having at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably.

In formulas (I) and (II),
R ₁ and R ₃ each independently represent a hydrogen atom, an optionally substituted methyl group, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group.
R ₂ , R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.

R ₁ and R ₃ preferably represent a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Specific examples and preferred examples of the monovalent organic group in R ₉ are the same as those described for R ₉ in formula (AI).

The alkyl group in R ₂ may be linear or branched, and may have a substituent.
The cycloalkyl group in R ₂ may be monocyclic or polycyclic and may have a substituent.
R ₂ is preferably an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.

  R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R together with the carbon atom is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6.

R ₃ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

The alkyl group in R ₄ , R ₅ , and R ₆ may be linear or branched and may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

As a repeating unit represented by general formula (I), the repeating unit represented by the following general formula (1-a) is mentioned, for example.

In the formula, _{R 1} and _{R 2} have the same meanings as those in formula (I).

The repeating unit represented by the general formula (II) is preferably a repeating unit represented by the following general formula (II-1).

In formula (II-1),
R _{3 to} R ₅ are respectively synonymous with those in the general formula (II).
R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent containing a polar group include a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group itself, or a linear or branched alkyl group or cycloalkyl group having at least one of them. An alkyl group having a hydroxyl group is preferable. More preferably, it is a branched alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

  The acid-decomposable resin is a resin containing at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably. In another embodiment, a resin containing at least two kinds of repeating units represented by the general formula (I) as the repeating unit represented by the general formula (AI) is more preferable.

The resin (B) may have one type of repeating unit having an acid-decomposable group, or two or more types may be used in combination. Preferred examples of the combination used are as follows. In the following formula, each R independently represents a hydrogen atom or a methyl group.

The resin (B) preferably further contains a repeating unit having a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or sultone structure, and other ring structures in the form of forming a bicyclo structure or a spiro structure in the 5- to 7-membered lactone structure or sultone structure. Is preferably a condensed ring. It is more preferable to have a repeating unit having a lactone structure or a sultone structure represented by any of the following general formulas (LC1-1) to (LC1-17), (SL1-1) and (SL1-2). A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), and more preferably (LC1-4). By using a specific lactone structure or sultone structure, substrate adhesion, LWR, development defects, and the like are improved.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .
In one embodiment, the resin (B) preferably contains a repeating unit represented by the following general formula (AII ′) as a repeating unit having a lactone structure or a sultone structure.

In general formula (AII ′),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

V represents a monovalent organic group containing a lactone structure or a sultone structure. Preferably, it represents a group having a structure represented by any of the general formulas (LC1-1) to (LC1-17), (SL1-1) and (SL1-2) shown above.
Specific examples of the repeating unit having a lactone group or a sultone group represented by the general formula (AII ′) are shown below, but the present invention is not limited thereto.
In the following formulae, Me represents a methyl group.

As the particularly preferred repeating unit having a lactone group or sultone group represented by the general formula (AII ′), the following repeating units may be mentioned. By selecting an optimal lactone group or sultone group, the pattern profile and the density dependency are improved.

In another embodiment, the resin (B) preferably contains a repeating unit represented by the following general formula (III) as a repeating unit having a lactone structure or a sultone structure.

In formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof independently when there are a plurality of R ₀ .
When there are a plurality of Zs, each independently represents an ether bond, an ester bond, an amide bond, or a urethane bond.

Or urea bond

Represents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.

n is the repeating number of the structure represented by —R ₀ —Z—, represents an integer of 1 to 5, and is preferably 1.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.
The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a mercapto group, and a hydroxy group. Group, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, alkoxy group such as benzyloxy group, acyl group such as acetyl group and propionyl group, and acetoxy group. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

Preferable chain alkylene group in R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. Preferred cycloalkylene is cycloalkylene having 3 to 20 carbon atoms, and examples thereof include cyclohexylene, cyclopentylene, norbornylene, adamantylene and the like. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.

The substituent having a lactone structure or sultone structure represented by R ₈ is not limited as long as it has a lactone structure or sultone structure. As specific examples, the general formulas (LC1-1) to (LC1) described above are used. -17), lactone structures or sultone structures represented by (SL1-1) and (SL1-2) can be mentioned, and among these, the structure represented by (LC1-4) is particularly preferable. Further, n ₂ in (LC1-1) to (LC1-17), (SL1-1) and (SL1-2) is more preferably 2 or less.

R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) or a sultone structure (cyanosultone) having a cyano group as a substituent is more preferable.

Specific examples of the repeating unit having a group having a lactone structure or a sultone structure represented by the general formula (III) are shown below, but the present invention is not limited thereto.
In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

As the repeating unit having a lactone structure or a sultone structure represented by the general formula (III), a repeating unit represented by the following general formula (III-1) or (III-1 ′) is more preferable.

In general formulas (III-1) and (III-1 ′),
R ₇ , A, R ₀ , Z and n have the same meaning as in the general formula (III).

R ₇ ′, A ′, R ₀ ′, Z ′ and n ′ have the same meanings as R ₇ , A, R ₀ , Z and n in the general formula (III), respectively.

R ₉ independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group when there are a plurality of R _{9 s, and} when there are a plurality of R _{9 s} , May be formed.

R ₉ ′ independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, and when there are a plurality of R ₉ ′, two R ₉ ′ are bonded to each other. , May form a ring.

X and X ′ each independently represents an alkylene group, an oxygen atom or a sulfur atom.
m and m ′ each independently represents the number of substituents and represents an integer of 0 to 5. m and m ′ are preferably each independently 0 or 1.

The alkyl group for R ₉ and R ₉ ′ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. These groups may have a substituent, and examples of the substituent include an alkoxy group such as a hydroxy group, a methoxy group, and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom. R ₉ and R ₉ ′ are more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.

  Examples of the alkylene group for X and X ′ include a methylene group and an ethylene group. X and X ′ are preferably an oxygen atom or a methylene group, and more preferably a methylene group.

When m and m ′ are 1 or more, at least one of R ₉ and R ₉ ′ is preferably substituted at the α-position or β-position of the carbonyl group of the lactone or the sulfonyl group of sultone, particularly substituted at the α-position. It is preferable.

Although the specific example of the repeating unit which has group which has lactone structure or sultone structure represented by general formula (III-1) or (III-1 ') is shown, this invention is not limited to this. In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

  The repeating unit having a lactone group or a sultone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

  In order to enhance the effect of the present invention, two or more repeating units having a lactone group or a sultone group may be used in combination. In this case, it is preferable to use two or more kinds of lactone or sultone repeating units selected from general formula (III) in combination, and in particular, two kinds of lactone or sultone repeating units in which n is 1 in general formula (III). The above is preferably selected and used in combination.

  The content of the repeating unit having a lactone structure or a sultone structure is preferably 15 to 60 mol%, more preferably 20 to 60 mol%, based on all repeating units in the resin (B) in the case where a plurality of types are contained. More preferably, it is 30-60 mol%.

The resin (B) is a repeating unit other than the general formulas (AI) and (III), and preferably has a repeating unit having a hydroxyl group or a cyano group. This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

In general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms.

Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c.

  The content of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (B).

Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

  The resin (B) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron-withdrawing group at the α-position. It is more preferable to have a repeating unit. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain. Both are preferable, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

As for the content rate of the repeating unit which has an alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in resin (B), More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.
Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The resin (B) of the present invention further has an alicyclic hydrocarbon structure that does not have a polar group (for example, the alkali-soluble group, hydroxyl group, cyano group, etc.) and has a repeating unit that does not exhibit acid decomposability. it can. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group. Groups. Preferable monocyclic hydrocarbon groups are monocyclic hydrocarbon groups having 3 to 7 carbon atoms, and more preferable examples include a cyclopentyl group and a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group described above may further have a substituent, and examples of the substituent that may further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. The group can be mentioned.

  Examples of the group in which the hydrogen atom is substituted include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The resin (B) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. The content of is preferably 1 to 40 mol%, more preferably 2 to 20 mol%, based on all repeating units in the resin (B).
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  Resin (B) used in the composition of the present invention has, in addition to the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolving power which is a general necessary characteristic of resist. It can have various repeating structural units for the purpose of adjusting heat resistance, sensitivity and the like.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

  Thereby, performance required for the resin used in the composition of the present invention, in particular, (1) solubility in coating solvent, (2) film-forming property (glass transition point), (3) alkali developability, (4 Fine adjustments such as () film slippage (selection of hydrophilicity / hydrophobicity, alkali-soluble group), (5) adhesion of unexposed part to substrate, (6) dry etching resistance, etc. are possible.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin (B) used in the composition of the present invention, the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist performance required. It is appropriately set to adjust the resolving power, heat resistance, sensitivity and the like.

When the composition of the present invention is used for ArF exposure, the resin (B) used in the composition of the present invention preferably has substantially no aromatic group from the viewpoint of transparency to ArF light. . More specifically, the repeating unit having an aromatic group is preferably 5% by mole or less, more preferably 3% by mole or less, and more preferably 3% by mole or less of the entire repeating unit of the resin (B). More preferably, it is 0 mol%, that is, it does not have a repeating unit having an aromatic group.
The resin (B) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In addition, it is preferable that resin (B) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin (HR) mentioned later.

  The resin (B) used in the composition of the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units. Moreover, the alicyclic hydrocarbon substituted by the (meth) acrylate type repeating unit 20-50 mol% which has an acid-decomposable group, the (meth) acrylate type repeating unit 20-50 mol% which has a lactone group, and a hydroxyl group or a cyano group. A copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a structure and further containing 0 to 20 mol% of another (meth) acrylate-based repeating unit is also preferred.

  When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (B) further has a hydroxystyrene-based repeating unit. It is preferable. More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such as a (meth) acrylic acid tertiary alkyl ester.

  Examples of the repeating unit having a preferred acid-decomposable group based on hydroxystyrene include, for example, t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, a repeating unit of (meth) acrylic acid tertiary alkyl ester, and the like. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

  The resin (B) in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

  The weight average molecular weight of the resin (B) of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3, as a polystyrene conversion value by GPC method. 000 to 15,000, particularly preferably 3,000 to 12,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

  The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. Those in the range are used. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

In the present invention, the content of the resin (B) in the entire composition is preferably from 30 to 99 mass%, more preferably from 60 to 95 mass%, based on the total solid content.
In addition, the resins of the present invention may be used alone or in combination.

  In addition, you may use other resin other than resin (B) in this invention in the range which does not impair the effect of this invention. Examples of the resin other than the resin (B) in the present invention include an acid-decomposable resin that may contain a repeating unit that can be contained in the resin (B), and other known acid-decomposable resins. be able to.

[3] Compound (C) that generates acid upon irradiation with active light or radiation
The composition of the present invention preferably further contains a compound capable of generating an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator” or “compound (C)”). Compound (C) is different from the aforementioned compound (A).

Although it will not specifically limit as an acid generator if it is a well-known thing, Preferably the compound represented by the following general formula (ZI), (ZII), (ZIII) can be mentioned.

In general formula (ZI):
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 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. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (ZI) is a single bond or at least one of R _{201 to} R ₂₀₃ of another compound represented by the general formula (ZI) It may be a compound having a structure bonded through a linking group.
Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

  The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.

  The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

Examples of other Z ⁻ include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony (for example, SbF ₆ ⁻ ), and the like.

Z ^- The at least α-position by an aliphatic sulfonate anion substituted with a fluorine atom, a fluorine atom or a fluorine atom is substituted with a group having a aromatic sulfonate anion of a sulfonic acid, an alkyl group substituted with a fluorine atom Bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.

  From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), and a cycloalkyl group (having 3 carbon atoms). ~ 15 are preferred).

Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.

These aryl groups, alkyl groups and cycloalkyl groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

Two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like, but are not limited thereto.

Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0046 and 0047 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, US Compounds exemplified as formulas (I-1) to (I-70) in Patent Publication No. 2003 / 0224288A1, and Formulas (IA-1) to (I) in U.S. Patent Publication No. 2003 / 0077540A1 IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).

In particular, when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group, the following aspect (1) or (2) is particularly preferable.

(1) At least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a structure represented by Ar—CO—X—, and the remaining group is a linear or branched alkyl group or a cycloalkyl group. If. At this time, when there are two remaining groups, two linear or branched alkyl groups or cycloalkyl groups may be bonded to each other to form a ring structure.

Here, Ar represents an aryl group which may have a substituent, and is specifically the same as the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ . A phenyl group which may have a substituent is preferable.

  X represents an alkylene group which may have a substituent. Specifically, it is an alkylene group having 1 to 6 carbon atoms. Preferably it is a C1-C3 linear or branched alkylene group.

  The remaining linear or branched alkyl group or cycloalkyl group preferably has 1 to 6 carbon atoms. These atomic groups may further have a substituent. Moreover, when the remaining groups are two, it is preferable that they are bonded to each other to form a ring structure (preferably a 5- to 7-membered ring).

(2) One or two of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are an aryl group which may have a substituent, and the remaining group is a linear or branched alkyl group or a cycloalkyl group If there is.

In this case, the aryl group is specifically the same as the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , and is preferably a phenyl group or a naphthyl group. The aryl group preferably has any one of a hydroxyl group, an alkoxy group, and an alkyl group as a substituent. More preferably, it is a C1-C12 alkoxy group as a substituent, More preferably, it is a C1-C6 alkoxy group.

  The remaining linear or branched alkyl group or cycloalkyl group preferably has 1 to 6 carbon atoms. These atomic groups may further have a substituent. When the remaining groups are two, the two may be bonded to each other to form a ring structure.

  More preferable examples of the (ZI) component include compounds (ZI-3) and (ZI-4) described below.

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

In general formula (ZI-3),
R _{1c to} R _5c are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.

R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. In addition, this ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.

  Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3 to 10 membered rings.

Zc ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

The alkyl group as R _{1c to} R _7c may be either linear or branched, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms. Examples of cycloalkyl groups include Examples thereof include a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group).

The aryl group as R _{1c to} R _5c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, and examples thereof include linear and branched alkoxy groups having 1 to 10 carbon atoms and cyclic alkoxy groups having 3 to 10 carbon atoms. be able to.

Specific examples of the alkoxy group in the alkoxycarbonyl group as R _1c to R _5c are the same as specific examples of the alkoxy group of _R 1c _{to R 5c.}

Specific examples of the alkyl group in the alkylcarbonyloxy group and alkylthio group as R _1c to R _5c are the same as specific examples of the alkyl group of _R 1c _{to R 5c.}

Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R _1c to R _5c are the same as specific examples of the cycloalkyl group of _R 1c _{to R 5c.}

Specific examples of the aryl group in the aryloxy group and arylthio group as R _1c to R _5c are the same as specific examples of the aryl group of _R 1c _{to R 5c.}

Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group.

The ring structure that any two or more of R _{1c to} R _5c may be bonded to each other is preferably a 5-membered or 6-membered ring.

The ring structure which may be formed by R _5c and R _6c are bonded to each other, bonded R _5c and R _6c are each other a single bond or an alkylene group (methylene group, ethylene group, etc.) by configuring the generally Examples thereof include a carbonyl carbon atom in formula (ZI-3) and a 4-membered ring (particularly preferably a 5- to 6-membered ring) formed together with the carbon atom.

The aryl group as R _6c and R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

As an aspect of R _6c and R _7c , it is preferable that both of them are alkyl groups.

The ring formed by combining R _6c and R _7c may have a hetero atom such as an oxygen atom in the ring.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c .

_Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group as R _x and R _y include a group having> C═O at the 2-position of the alkyl group and cycloalkyl group as R _{1c to} R _7c. .

As for the alkoxy group in the alkoxycarbonylalkyl group as R _x and R _y , the same alkoxy group as in R _{1c to} R _5c can be exemplified, and the alkyl group is, for example, a linear chain having 1 to 12 carbon atoms. An alkyl group can be mentioned.

The allyl group as R _x and R _y is not particularly limited, but is preferably an unsubstituted allyl group or an allyl group substituted with a monocyclic or polycyclic cycloalkyl group.

The vinyl group as R _x and R _y is not particularly limited, but is preferably an unsubstituted vinyl group or a vinyl group substituted with a monocyclic or polycyclic cycloalkyl group.

The ring structure which may be formed by R _5c and R _x are bonded to each other by R _5c and R _x constitutes a bond to a single bond or an alkylene group with one another, formula (ZI-3) in the Examples thereof include a 5-membered ring (particularly preferably a 5-membered ring) formed with a sulfur atom and a carbonyl carbon atom.

As the ring structure which R _x and R _y may combine with each other, a 5-membered or 6-membered ring formed by divalent R _x and R _y together with a sulfur atom in the general formula (ZI-3) Is mentioned.

R _x and R _y are preferably an alkyl group or a cycloalkyl group having 4 or more carbon atoms.

R _{1c to} R _7c , R _x and R _y may further have a substituent, and examples of such a substituent include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cyclo group. Alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, etc. Can be mentioned.

Next, the compound (ZI-4) will be described.
The compound (ZI-4) is represented by the following general formula (ZI-4).

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.

When there are a plurality of R _{14 s,} each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Represent. These groups may have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. These groups may have a substituent.

l represents an integer of 0-2.
r represents an integer of 0 to 8.

Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

In General Formula (ZI-4), the alkyl groups represented by R ₁₃ , R _14, and R ₁₅ are linear or branched and preferably have 1 to 10 carbon atoms.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group.

The alkoxy group for R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms.

The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms.

Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

The alkyl group of the alkyl group of R _14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

The alkylsulfonyl group and cycloalkylsulfonyl group for R ₁₄ are linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms.

  Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Etc.

As a ring structure that two R ₁₅ may be bonded to each other, a 5-membered or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the general formula (ZI-4) is particularly preferable. Includes a 5-membered ring (that is, a tetrahydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxy group. Examples thereof include a carbonyl group and an alkoxycarbonyloxy group. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.

R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two R ^15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.
The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

  Specific examples of the cation structure possessed by the compounds (ZI-3) and (ZI-4) described above include the above-mentioned JP-A Nos. 2004-233661, 2003-35948, and US Patent Application Publication No. 2003. In addition to cation structures such as compounds exemplified in the specification of U.S. Pat. No. 0224288A1 and U.S. Patent Application Publication No. 2003 / 0077540A1, for example, paragraphs 0046, 0047, 0072 to 0077, 0107 Cation structure in the chemical structure and the like exemplified in .about.0110, and the cation structure in the chemical structure and the like exemplified in paragraphs 0135 to 0137, 00151, and 0196 to 0199 in JP2011-53430A.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Even the substituent, an aryl group of R ₂₀₁ to R ₂₀₃ in the above compound (ZI), alkyl groups include those which may have a cycloalkyl group.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

Specific examples of the aryl group represented by Ar ₃ , Ar ₄ , R ₂₀₈ , R _209, and R ₂₁₀ include the same examples as the specific examples of the aryl group as R _{201 to} R ₂₀₃ in the general formula (ZI). it can.

Specific examples of the alkyl group and cycloalkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the alkyl group and cycloalkyl group as R _{201 to} R ₂₀₃ in the general formula (ZI), respectively. Can be mentioned.

  The alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 carbon atoms. ˜12 alkenylene groups (for example, vinylene group, propenylene group, butenylene group, etc.), and as the arylene group for A, arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Each can be mentioned.

One preferred embodiment of the present invention is that the acid generator is represented by the following general formula (I ′). By being represented by the following general formula (I ′), the light transmittance of the exposed film is improved, which can contribute to the improvement of LWR and DOF.

In the general formula (I ′),
X ′ represents an oxygen atom, a sulfur atom or —N (Rx ′) —.

R ₁ ′ to R ₉ ′ and Rx ′ have the same meanings as R _{1 to} R ₉ and Rx in the general formula (I), respectively.

R ₁ ′ and R ₂ ′ may be connected to each other to form a ring. In addition, any two or more of R ₆ ′ to R ₉ ′, R ₃ ′ and R ₉ ′, R ₄ ′ and R ₅ ′, R ₅ ′ and Rx ′, R ₆ ′ and Rx ′, They may be connected to each other to form a ring.

  Moreover, in the composition of this invention, it is preferable that the structure of the cation part of an acid generator is the same as the structure of the cation part of a compound (A). As described above, by making the cation structure of the acid generator the same as the cation structure of the compound (A), an unintended ion exchange reaction can be prevented.

Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.
Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the composition is preferably 0.1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 7 to 20% by mass based on the total solid content in the composition. It is.

[4] Hydrophobic resin (HR)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (HR)”), particularly when applied to immersion exposure. . As a result, the hydrophobic resin (HR) is unevenly distributed on the surface layer of the film, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to.

  Hydrophobic resin (HR) is unevenly distributed at the interface as described above, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances should be mixed uniformly. It does not have to contribute to

  The hydrophobic resin typically contains fluorine atoms and / or silicon atoms. The fluorine atom and / or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin or may be contained in the side chain.

  When the hydrophobic resin contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. preferable.

  The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, You may have the substituent of.

  The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.

  Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and the aryl group may further have another substituent.

As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom, a group represented by any one of the following general formulas (F2) to (F4) is preferable. However, the present invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (straight or branched). Provided that at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ and at least one of R _{65 to} R ₆₈ are a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. (Preferably having 1 to 4 carbon atoms).

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably a fluoroalkyl group (preferably having 1 to 4 carbon atoms), and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. When R ₆₂ and _{R 63} is a perfluoroalkyl _group, it is preferred that _{R 64} is a hydrogen atom. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

  Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

  Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH _(CF 3) OH and the like, -C _{(CF 3)} 2 OH is preferred.

The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more.
Suitable examples of the repeating unit having a fluorine atom include those shown below.

In the formula, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.

W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

In addition to these, the hydrophobic resin may have a unit as shown below as a repeating unit having a fluorine atom.

In the formula, R _{4 to} R ₇ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.
However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.
W ₂ represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or alkyl), —NHSO ₂ — or a divalent linking group in which a plurality of these are combined.

  Q represents an alicyclic structure. The alicyclic structure may have a substituent, may be monocyclic, may be polycyclic, and may be bridged in the case of polycyclic. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, norbornyl group, dicyclopentyl group. , Tricyclodecanyl group, tetocyclododecyl group and the like. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom. Particularly preferred examples of Q include a norbornyl group, a tricyclodecanyl group, a tetocyclododecyl group, and the like.

The hydrophobic resin may contain a silicon atom.
The partial structure having a silicon atom preferably has an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. The divalent linking group includes an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, or a group of two or more groups selected from the group consisting of a ureylene bond. A combination is mentioned.

  n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

  The repeating unit having at least either a fluorine atom or a silicon atom is preferably a (meth) acrylate-based repeating unit.

Hereinafter, although the specific example of the repeating unit which has at least any one of a fluorine atom and a silicon atom is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ , and X ₂ represents —F or —CF ₃ .

  The hydrophobic resin preferably has a repeating unit (b) having at least one group selected from the group consisting of the following (x) to (z).

(X) Alkali-soluble group (y) A group that decomposes by the action of an alkali developer and increases the solubility in an alkali developer (hereinafter also referred to as a polar conversion group).
(Z) A group that decomposes by the action of an acid to increase the solubility in an alkali developer. Examples of the repeating unit (b) include the following types.

A repeating unit (b ′) having at least one of a fluorine atom and a silicon atom and at least one group selected from the group consisting of the above (x) to (z) on one side chain
A repeating unit (b *) having at least one group selected from the group consisting of (x) to (z) and having no fluorine atom and no silicon atom
A fluorine atom and silicon on one side chain having at least one group selected from the group consisting of (x) to (z) above and on a side chain different from the side chain in the same repeating unit Repeating unit (b ″) having at least one of atoms
It is more preferable that the hydrophobic resin has a repeating unit (b ′) as the repeating unit (b). That is, it is more preferable that the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has at least one of a fluorine atom and a silicon atom.

  When the hydrophobic resin has a repeating unit (b *), a repeating unit having at least one of a fluorine atom and a silicon atom (a repeating unit different from the repeating units (b ′) and (b ″)) In addition, in the repeating unit (b ″), the side chain having at least one group selected from the group consisting of the following (x) to (z), and at least one of a fluorine atom and a silicon atom Are preferably bonded to the same carbon atom in the main chain, that is, in a positional relationship as shown in the following formula (K1).

In the formula, B1 represents a partial structure having at least one group selected from the group consisting of the above (x) to (z), and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

  The group selected from the group consisting of the above (x) to (z) is preferably (x) an alkali-soluble group or (y) a polar conversion group, and more preferably (y) a polar conversion group.

  Examples of the alkali-soluble group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.

  Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

  As the repeating unit (bx) having an alkali-soluble group (x), a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a linking group is used. Examples include a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be used at the time of polymerization to be introduced at the end of the polymer chain, Either case is preferred.

  In the case where the repeating unit (bx) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, corresponding to the repeating unit (b ′) or (b ″)), the repeating unit (bx) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (bx) is the same as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

  The content of the repeating unit (bx) having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol, based on all repeating units in the hydrophobic resin. %.

Specific examples of the repeating unit (bx) having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Examples of the polar conversion group (y) include a lactone group, a carboxylic acid ester group (—COO—), an acid anhydride group (—C (O) OC (O) —), an acid imide group (—NHCONH—), A carboxylic acid thioester group (—COS—), a carbonic acid ester group (—OC (O) O—), a sulfate ester group (—OSO ₂ O—), a sulfonic acid ester group (—SO ₂ O—), and the like. A lactone group is preferred.

  The polarity converting group (y) is, for example, introduced into the side chain of the resin by being included in a repeating unit of acrylic acid ester or methacrylic acid ester, or a polymerization initiator or chain having the polarity converting group (y). Any form in which a transfer agent is introduced at the end of the polymer chain using the polymerization is preferred.

  Specific examples of the repeating unit (by) having a polar conversion group (y) include a repeating unit having a lactone structure represented by formulas (KA-1-1) to (KA-1-17) described later. Can do.

  Further, the repeating unit (by) having the polarity converting group (y) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, the repeating unit (b ′), (b ″) corresponds to the repeating unit (b ′)). The resin having the repeating unit (by) is hydrophobic, but is particularly preferable from the viewpoint of reducing development defects.

As the repeating unit (by), for example, a repeating unit represented by the formula (K0) can be given.

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.

R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.

However, at least one of R _k1 and R _k2 represents a group containing a polarity converting group.

The polarity converting group represents a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer as described above. The polar conversion group is preferably a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH—, Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.

Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.

The repeating unit (by) has a group that increases the solubility in a preferable alkali developer by having a group having a partial structure represented by the general formula (KA-1) or (KB-1). Are bonded to each other as in the case of the partial structure represented by the general formula (KA-1) and the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent When it does not have a hand, the group having the partial structure is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the partial structure.

  The partial structure represented by the general formula (KA-1) or (KB-1) is linked to the main chain of the hydrophobic resin through a substituent at an arbitrary position.

  The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure with the group as X.

  X in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, or a carbonic acid ester group. More preferably, it is a carboxylic acid ester group.

The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .

Z _ka1 independently represents a halogen atom, an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group, when there are a plurality of Z _ka1 .

Z _ka1 may be linked to form a ring. Examples of the ring formed by connecting Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).

  nka represents an integer of 0 to 10. Preferably it is an integer of 0 to 8, more preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

The electron withdrawing group as Z _{ka1 is the same} as the electron withdrawing group as Y ¹ and Y ² described later. The electron withdrawing group may be substituted with another electron withdrawing group.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron withdrawing group, and more preferably an alkyl group, a cycloalkyl group, or an electron withdrawing group. In addition, as an ether group, the thing substituted by the alkyl group or the cycloalkyl group, ie, the alkyl ether group, etc. are preferable. The electron withdrawing group has the same meaning as described above.

Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group as Z _ka1 may have a substituent and may be linear or branched. As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl. Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. As a branched alkyl group, Preferably it is C3-C30, More preferably, it is 3-20, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like. C1-C4 things, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, are preferable.

The cycloalkyl group as Z _ka1 may have a substituent, and may be monocyclic or polycyclic. In the case of a polycyclic type, the cycloalkyl group may be a bridged type. That is, in this case, the cycloalkyl group may have a bridged structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, Examples thereof include a camphanyl group, a dicyclopentyl group, an α-pinanyl group, a tricyclodecanyl group, a tetocyclododecyl group, and an androstanyl group. As the cycloalkyl group, the following structure is also preferable. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

  Preferred examples of the alicyclic moiety include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group. And cyclododecanyl group. More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.

  Examples of the substituent of these alicyclic structures include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group. Preferred examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the substituent that the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).

  Further, the above group may further have a substituent, and examples of the further substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, and a methoxy group. , Ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, Aralkyl group such as benzyl group, phenethyl group, cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, vinyl group, propenyl Group, alkenyl group such as allyl group, vinyloxy group, propenyl Alkoxy group include an allyloxy group, an alkenyloxy group such as a butenyloxy group, a phenyl group, an aryl group such as a naphthyl group, an aryloxy group such as phenoxy group, aryloxycarbonyl group such as benzoyloxy group.

  X in the general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by the general formula (KA-1) is preferably a lactone ring, and more preferably a 5- to 7-membered lactone ring.

In addition, as in the following (KA-1-1) to (KA-1-17), a 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1) has a bicyclo structure, a spiro It is preferred that other ring structures are condensed in a form that forms the structure.
As for the peripheral ring structure to which the ring structure represented by the general formula (KA-1) may be bonded, for example, those in the following (KA-1-1) to (KA-1-17), or The thing according to can be mentioned.

As a structure containing a lactone ring structure represented by the general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. The lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14) and (KA-1-17).

The structure containing the lactone ring structure may or may not have a substituent. Preferable substituents include those similar to the substituent Z _ka1 that the ring structure represented by the general formula (KA-1) may have.
Preferred examples of X in the general formula (KB-1) include a carboxylic acid ester group (—COO—).
Y ¹ and Y ² in formula (KB-1) each independently represent an electron-withdrawing group.

The electron withdrawing group is a partial structure represented by the following formula (EW). * In the formula (EW) represents a bond directly connected to (KA-1) or a bond directly connected to X in (KB-1).

In formula (EW),
n _ew is the repeating number of the linking group represented by —C (R _ew1 ) (R _ew2 ) — and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond, indicating that Y _ew1 is directly bonded.

Y _ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo (cyclo) alkyl group or a haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , an oxy group, a carbonyl group, a sulfonyl group Examples thereof include a group, a sulfinyl group, and a combination thereof. The electron-withdrawing group may have the following structure, for example. The “halo (cyclo) alkyl group” represents an alkyl group and a cycloalkyl group that are at least partially halogenated, and the “haloaryl group” represents an aryl group that is at least partially halogenated. In the following structural formula, R _ew3 and R _ew4 each independently represent an arbitrary structure. R _ew3 and R _ew4 may have any structure, and the partial structure represented by the formula (EW) may have an electron withdrawing property, and may be linked to, for example, the main chain of the resin. An alkyl group and a fluorinated alkyl group;

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with an arbitrary atom or substituent. At least one group of Y _ew1 , R _ew1 , and R _ew2 may be connected to the main chain of the hydrophobic resin through a further substituent.

Y _ew1 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 .

R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group. Represents a fluoromethyl group.

R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.

R _{f1 to} R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.
Examples of the (halo) alkyl group in R _{f1 to} R _f3 include the alkyl group in Z _ka1 described above and a structure in which this is halogenated.

Examples of the (per) halocycloalkyl group and the (per) haloaryl group in R _{f1 to} R _f3 or in the ring formed by linking R _f2 and R _f3 include, for example, the aforementioned cycloalkyl group in Z _ka1 is a halogen atom. And a perfluoroaryl group represented by -C _(n) F _(n-1) and more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H Can be mentioned. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.

The ring that may be formed by linking at least two of R _ew1 , R _ew2 and Y _ew1 preferably includes a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).

  In the repeating unit (by), a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or a general formula (KA) It may have both a partial structure represented by -1) and a partial structure represented by the general formula (KB-1).

Note that part or all of the partial structure of the general formula (KA-1) may also serve as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group functions as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). There is also a possibility.

In addition, when the repeating unit (by) corresponds to the repeating unit (b *) or the repeating unit (b ″) and has a partial structure represented by the general formula (KA-1), the general formula (KA) As for the partial structure represented by -1), it is more preferable that the polarity conversion group is a partial structure represented by -COO- in the structure represented by the general formula (KA-1).
The repeating unit (by) can be a repeating unit having a partial structure represented by the general formula (KY-0).

In the general formula (KY-0),
R ₂ represents a chain or cyclic alkylene group, and when there are a plurality of R ₂ groups, they may be the same or different.

R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbons are substituted with fluorine atoms.

R ₄ is a halogen atom, cyano group, hydroxy group, amide group, alkyl group, cycloalkyl group, alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). When there are a plurality of R _{4 s} , they may be the same or different, and two or more R ₄ may be bonded to form a ring.

  X represents an alkylene group, an oxygen atom, or a sulfur atom.

  Z and Za represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of them, they may be the same or different.

  * Represents a bond to the main chain or side chain of the resin.

o is the number of substituents and represents an integer of 1 to 7.
m is the number of substituents and represents an integer of 0 to 7.
n represents the number of repetitions and represents an integer of 0 to 5.

The structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) ₁ —COO— (l represents an integer of 1 to 5).
The preferred carbon number range and specific examples of the chain or cyclic alkylene group as R ₂ are the same as those described for the chain alkylene group and cyclic alkylene group in Z ₂ of the general formula (bb).

The linear, branched or cyclic hydrocarbon group as R ₃ has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and preferably 3 carbon atoms when branched. -30, more preferably 3-20, and in the case of a ring, it is 6-20. Specific examples of R ₃ include specific examples of the alkyl group and cycloalkyl group as Z _ka1 described above.

Preferred carbon numbers and specific examples of the alkyl group and cycloalkyl group as R ₄ and R are the same as those described in the alkyl group and cycloalkyl group as Z _ka1 described above.

The acyl group as R ₄ is preferably one having 1 to 6 carbon atoms, and examples thereof include a formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, and pivaloyl group.

Examples of the alkyl moiety in the alkoxy group and alkoxycarbonyl group as R ₄ include a linear, branched or cyclic alkyl moiety, and the preferred carbon number of the alkyl moiety and specific examples thereof are those described above for Z _ka1. The same as those described in the alkyl group and cycloalkyl group.

Examples of the alkylene group as X include a chain or cyclic alkylene group, and preferred carbon numbers and specific examples thereof are the same as those described for the chain alkylene group and cyclic alkylene group as R ₂ .

Moreover, the repeating unit which has a partial structure shown below as a specific structure of a repeating unit (by) is mentioned.

In general formulas (rf-1) and (rf-2),
X ′ represents an electron-withdrawing substituent, preferably a carbonyloxy group, an oxycarbonyl group, an alkylene group substituted with a fluorine atom, or a cycloalkylene group substituted with a fluorine atom.

  A represents a single bond or a divalent linking group represented by -C (Rx) (Ry)-. Here, Rx and Ry are each independently a hydrogen atom, a fluorine atom, an alkyl group (preferably having 1 to 6 carbon atoms and optionally substituted with a fluorine atom or the like), or a cycloalkyl group (preferably a carbon atom). And may be substituted with a fluorine atom or the like. Rx and Ry are preferably a hydrogen atom, an alkyl group, or an alkyl group substituted with a fluorine atom.

X represents an electron withdrawing group, and specific examples thereof include the above-mentioned electron withdrawing groups as Y ¹ and Y ² , preferably a fluorinated alkyl group or a fluorinated cycloalkyl group. An aryl group substituted with a fluorine or fluorinated alkyl group, an aralkyl group substituted with a fluorine or fluorinated alkyl group, a cyano group, or a nitro group.

  * Represents a bond to the main chain or side chain of the resin. That is, it represents a bond that binds to the resin main chain through a single bond or a linking group.

  In addition, when X 'is a carbonyloxy group or an oxycarbonyl group, A is not a single bond.

  When the polarity conversion group is decomposed by the action of the alkali developer and the polarity is changed, the receding contact angle with water of the resist film after alkali development can be lowered. It is preferable from the viewpoint of suppressing development defects that the receding contact angle with water of the film after alkali development is lowered.

  The receding contact angle with water of the resist film after alkali development is preferably 50 ° or less at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, more preferably 40 ° or less, still more preferably 35 ° or less. Most preferably, it is 30 ° or less.

  The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.

  The hydrolysis rate of the hydrophobic resin with respect to the alkaline developer is preferably 0.001 nm / second or more, more preferably 0.01 nm / second or more, still more preferably 0.1 nm / second or more, Most preferably, it is 1 nm / second or more.

  Here, the hydrolysis rate of the hydrophobic resin with respect to the alkaline developer was 23 ° C. when TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%) was used to form the resin film with only the hydrophobic resin. This is the rate at which the film thickness decreases.

  The repeating unit (by) is more preferably a repeating unit having at least two or more polar conversion groups.

When the repeating unit (by) has at least two polar conversion groups, the repeating unit (by) preferably has a group having a partial structure having two polar conversion groups represented by the following general formula (KY-1). Note that when the structure represented by the general formula (KY-1) does not have a bond, it is a group having a monovalent or higher valent group in which at least one arbitrary hydrogen atom in the structure is removed.

In general formula (KY-1),
R _ky1 and R _ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and R _ky4 are bonded to the same oxygen atom to form a part of a carbonyl group (═O). May be formed.

R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include the same groups as those described above for Y ₁ and Y ₂ in the formula (KB-1), and preferably a halogen atom or the aforementioned —C (R _f1 ) (R _f2 ) —R _f3. A halo (cyclo) alkyl group or a haloaryl group represented by the formula: Preferably _{R ky3} halogen atom, or the _{-C (R f1)} (R f2) is represented by the halo (cyclo) alkyl groups or haloaryl groups _{-R f3,} lactone _{R ky2} is linked to _{R ky1} An electron withdrawing group that forms a ring or has no halogen atom.

R _ky1 , R _ky2 , and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.

Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka1 in formula (KA-1).

As the lactone ring formed by linking R _ky1 and R _ky2 , the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ₁ and Y ₂ in the formula (KB-1).

The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2). Note that the structure represented by the general formula (KY-2) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.

Two or more of R _{ky6 to} R _ky10 may be linked to each other to form a monocyclic or polycyclic structure.

R _ky5 represents an electron withdrawing group. Examples of the electron withdrawing group include the same groups as those described above for Y ₁ and Y ₂ , and preferably a halogen atom or a halo (cyclo (cyclo) represented by —C (R _f1 ) (R _f2 ) —R _f3 ) An alkyl group or a haloaryl group.

Specific examples of R _{ky5 to} R _ky10 include the same groups as Z _ka1 in formula (KA-1).

The structure represented by the formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).

In formula (KY-3), Z _ka1 and nka have the same meanings as those in formula (KA-1). R _ky5 has the same _{meaning as} in formula (KY-2).

L _ky represents an alkylene group, an oxygen atom or a sulfur atom. _Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

  The repeating unit (b) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation, etc., but is a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Preferably there is. Examples include acrylate-based repeating units (including those having substituents at the α-position and β-position), styrene-based repeating units (including those having substituents at the α-position and β-position), vinyl ether-based repeating units, norbornene-based Repeating units, maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), and the like, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units Preferred are acrylate repeat units, vinyl ether repeat units, and norbornene repeat units, with acrylate repeat units being most preferred.

  When the repeating unit (by) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit (by) corresponds to the repeating unit (b ′) or (b ″)), the repeating unit (by) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

  The content of the repeating unit (by) in the hydrophobic resin is preferably from 10 to 100 mol%, more preferably from 20 to 99 mol%, still more preferably from 30 to 97 mol%, based on all repeating units in the hydrophobic resin. Most preferably, it is 40-95 mol%.

Specific examples of the repeating unit (by) having a group capable of increasing the solubility in an alkali developer are shown below, but are not limited thereto. Moreover, what was mentioned as a specific example of the repeating unit (a3) of the said resin (A) can also be mentioned as a specific example of a repeating unit (by).
In the specific examples shown below, Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  Examples of the method for synthesizing the monomer corresponding to the repeating unit (by) having the polar conversion group (y) as described above include the method described in International Publication No. 2010/069705, International Publication No. 2010/069705, or the like. Can be synthesized with reference to

  In the hydrophobic resin, examples of the repeating unit (bz) having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group listed for the resin (A).

  In the case where the repeating unit (bz) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, corresponding to the repeating unit (b ′) or (b ″)), the repeating unit (bz) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

  In the hydrophobic resin, the content of the repeating unit (bz) having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably based on all repeating units in the hydrophobic resin. It is 10-80 mol%, More preferably, it is 20-60 mol%.

  Hereinabove, the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has been described, but the content of the repeating unit (b) in the hydrophobic resin is hydrophobic. It is preferably 1 to 98 mol%, more preferably 3 to 98 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 95 mol% with respect to all repeating units in the conductive resin.

  The content of the repeating unit (b ′) is preferably 1 to 100 mol%, more preferably 3 to 99 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 10 mol% with respect to all repeating units in the hydrophobic resin. 95 mol%.

  The content of the repeating unit (b *) is preferably from 1 to 90 mol%, more preferably from 3 to 80 mol%, still more preferably from 5 to 70 mol%, most preferably from 10 to 10%, based on all repeating units in the hydrophobic resin. 60 mol%. The content of the repeating unit having at least one of a fluorine atom and a silicon atom used together with the repeating unit (b *) is preferably 10 to 99 mol%, more preferably 20 with respect to all repeating units in the hydrophobic resin. It is -97 mol%, More preferably, it is 30-95 mol%, Most preferably, it is 40-90 mol%.

  The content of the repeating unit (b ″) is preferably 1 to 100 mol%, more preferably 3 to 99 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 10 mol% based on all repeating units in the hydrophobic resin. 95 mol%.

The hydrophobic resin may further have a repeating unit represented by the following general formula (CIII).

In general formula (CIII):
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a fluorine atom, a group containing a silicon atom, or the like.

L _c3 represents a single bond or a divalent linking group.
In general formula (CIII), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The aryl group is preferably a phenyl group or naphthyl group having 6 to 20 carbon atoms, and these may have a substituent.

R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).

It is also preferable that the hydrophobic resin further has a repeating unit represented by the following general formula (BII-AB).

In the formula (BII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

  When each group in the repeating unit represented by the general formula (III) or (BII-AB) is substituted with a group containing a fluorine atom or a silicon atom, the repeating unit includes at least the fluorine atom and the silicon atom. It corresponds also to the repeating unit which has either.

Specific examples of the repeating unit represented by the general formulas (III) and (BII-AB) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN. Note that the repeating unit in the case where Ra is CF ₃ also corresponds to the repeating unit having at least one of the fluorine atom and the silicon atom.

  As with the resin (B) described above, the hydrophobic resin naturally has few impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably 0. -5 mass%, 0-1 mass% is still more preferable. Thereby, a resist composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably, in terms of resolution, resist shape, resist pattern side walls, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

  As the hydrophobic resin, various commercially available products can be used, and can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.

  The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (B) described above.

Specific examples of the hydrophobic resin (HR) are shown below. Table 1 below shows the molar ratio of the repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains an actinic ray-sensitive or radiation-sensitive resin composition by containing a hydrophobic hydrophobic resin containing at least one of a fluorine atom and a silicon atom. When the hydrophobic resin is unevenly distributed in the surface layer of the film formed from the material and the immersion medium is water, the receding contact angle of the film surface after baking to water and before exposure is improved, and the immersion liquid followability is improved. Can be made.

  After baking the coating film comprising the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and before exposure, the receding contact angle of the film is the temperature at the time of exposure, usually room temperature 23 ± 3 ° C., humidity 45 ± 5%. 60 ° to 90 °, more preferably 65 ° or more, still more preferably 70 ° or more, and particularly preferably 75 ° or more.

  The hydrophobic resin is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule and contributes to uniform mixing of polar / nonpolar substances. It does not have to be.

  In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

  Hydrophobic resins are hydrophobic, so that development residues (scum) and BLOB defects are likely to deteriorate after alkali development, but they have three or more polymer chains via at least one branch, compared to linear resins. Further, since the alkali dissolution rate is improved, development residue (scum) and BLOB defect performance are improved.

  When the hydrophobic resin has a fluorine atom, the content of the fluorine atom is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mol% with respect to all the repeating units in hydrophobic resin, and it is more preferable that it is 30-100 mol%.

  When the hydrophobic resin has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the weight average molecular weight of the hydrophobic resin. Moreover, it is preferable that it is 10-90 mol% with respect to all the repeating units of hydrophobic resin, and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-80 mol%.

  The weight average molecular weight of the hydrophobic resin is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 35,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: tetrahydrofuran (THF)).

The content of the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive resin composition can be appropriately adjusted and used so that the receding contact angle of the actinic ray or radiation-sensitive resin film falls within the above range. Is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass, based on the total solid content of the light-sensitive or radiation-sensitive resin composition. And particularly preferably 0.2 to 8% by mass.
Hydrophobic resins can be used alone or in combination of two or more.

[5] Basic compound The actinic ray-sensitive or radiation-sensitive composition of the present invention preferably contains a basic compound.
The basic compound is preferably a nitrogen-containing organic basic compound.
The basic compound is different from the compound (A).

  Although the compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(4) is used preferably.

(1) Compound represented by the following general formula (BS-1)

In general formula (BS-1),
Each R independently represents a hydrogen atom, an alkyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, or an aralkyl group. However, not all three Rs are hydrogen atoms.

Although carbon number of the alkyl group as R is not specifically limited, Usually, 1-20, Preferably it is 1-12.
Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, 3-20, Preferably it is 5-15.

Although carbon number of the aryl group as R is not specifically limited, Usually, 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, 7-20, Preferably it is 7-11. Specific examples include a benzyl group.

  In the alkyl group, cycloalkyl group, aryl group or aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.

  In the compound represented by the general formula (BS-1), it is preferable that only one of three Rs is a hydrogen atom, or all Rs are not hydrogen atoms.

  Specific examples of the compound of the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N- Examples include dihexylaniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline.

  In addition, in the general formula (BS-1), a compound in which at least one R is an alkyl group substituted with a hydroxyl group is mentioned as one of preferable embodiments. Specific examples of the compound include triethanolamine and N, N-dihydroxyethylaniline.

The alkyl group as R may have an oxygen atom in the alkyl chain, and an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specific examples include tris (methoxyethoxyethyl) amine and compounds exemplified in column 3, line 60 and thereafter of US Pat. No. 6,040,112.

(2) Compound having a nitrogen-containing heterocyclic structure The heterocyclic structure may or may not have aromaticity. Moreover, you may have two or more nitrogen atoms, Furthermore, you may contain hetero atoms other than nitrogen. Specifically, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure (N-hydroxyethylpiperidine, bis (1,2,2,6) , 6-pentamethyl-4-piperidyl) sebacate), compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group has a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound. The phenoxy group is, for example, a substituent such as 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. You may have.

More preferably, it is a compound having at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is preferable.

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and US Patent Application Publication No. 2007 / 0224539A1. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above.

(4) Ammonium salt Ammonium salts are also used as appropriate. Preferred is hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable.

  In addition, examples of compounds that can be used in the composition of the present application include compounds synthesized in Examples of JP-A-2002-363146, compounds described in paragraph 0108 of JP-A-2007-298869, and the like.

A basic compound is used individually or in combination of 2 or more types.
The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of a composition, Preferably it is 0.01-5 mass%.

  The molar ratio of acid generator / basic compound is preferably 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. This molar ratio is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

[6] Low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid The composition of the present invention comprises a low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter referred to as “low molecular weight compound”). In this case, it is possible to contain “low molecular compound (D)” or “compound (D)”.

  The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.

  The molecular weight of the low molecular compound (F) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.

  As the compound (D), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

Compound (D) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. Rb may be bonded to each other to form a ring.

  The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are substituted with a functional group such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, alkoxy group, or halogen atom. It may be. The same applies to the alkoxyalkyl group represented by Rb.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group of Rb (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above functional group, alkoxy group, or halogen atom). )as,
For example, a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., a group derived from these alkanes, for example, A group substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group,
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, groups derived from these cycloalkanes, for example, methyl group, ethyl group, n-propyl group , I-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and other linear or branched alkyl groups substituted by one or more ,
Groups derived from aromatic compounds such as benzene, naphthalene, anthracene, etc., and groups derived from these aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 A group substituted with one or more linear or branched alkyl groups such as -methylpropyl group, 1-methylpropyl group, t-butyl group, and the like;
Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole, benzimidazole, and groups derived from these heterocyclic compounds are linear or branched A group substituted with one or more groups derived from an alkyl group or aromatic compound, a group derived from a linear or branched alkane, a group derived from a cycloalkane, a phenyl group, a naphthyl group , A group substituted with one or more groups derived from an aromatic compound such as anthracenyl group or the like, or the above substituent is a hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo And a group substituted with a functional group such as a group.

  Rb is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

  Examples of the ring formed by bonding two Rb to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.

The specific structure of the group represented by general formula (d-1) is shown below.

The compound (D) can also be constituted by arbitrarily combining the basic compound and the structure represented by the general formula (d-1).
The compound (D) particularly preferably has a structure represented by the following general formula (A).

The compound (D) may correspond to the above basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.

  In the general formula (A), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.

Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same. However, in -C (Rb) (Rb) (Rb), when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

  In the general formula (A), the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Ra are described above as the groups in which the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb may be substituted. It may be substituted with a group similar to the group.

  Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above groups) include: The same group as the specific example mentioned above about Rb is mentioned.

  Examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) or a derivative thereof formed by bonding of Ra to each other include, for example, pyrrolidine, piperidine, morpholine, 1, 4, 5 , 6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1, 2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2 , 5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene Groups derived from heterocyclic compounds such as indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, groups derived from these heterocyclic compounds A group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino And groups substituted with one or more functional groups such as a group, a morpholino group and an oxo group.

A particularly preferred compound (D) in the present invention is specifically shown, but the present invention is not limited thereto.

  The compound represented by the general formula (A) can be synthesized based on known methods described in JP-A-2007-298869, JP-A-2009-199021, and the like.

  In the present invention, (D) the low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid can be used singly or in combination of two or more.

  The composition of the present invention may or may not contain (D) a low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid. The rate is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the composition combined with the basic compound. It is.

  The ratio of the acid generator and the compound (D) used in the composition is preferably acid generator / [compound (D) + the above basic compound] (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / [compound (D) + basic compound] (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

[7] Surfactant The composition of the present invention may further contain a surfactant. When contained, the surfactant is preferably a fluorine-based and / or silicon-based surfactant.

  As surfactants corresponding to these, Megafac F176, Megafac R08 manufactured by DIC Corporation, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical Co., Ltd., manufactured by Sumitomo 3M Co., Ltd. Fluorado FC430, polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] et seq. Of US Patent Application Publication No. 2008 / 0248425A1.

  Surfactants may be used alone or in combination of two or more.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant, but when it is contained, the amount of surfactant used is actinic ray-sensitive or Preferably it is 0-2 mass% with respect to the total solid content (total quantity except a solvent) of a radiation sensitive resin composition, More preferably, it is 0.0001-2 mass%, Most preferably, it is 0.0005-1 mass%. is there.

  On the other hand, it is also preferable that the addition amount of the surfactant is 10 ppm or less or not contained. This increases the uneven distribution of the surface of the hydrophobic resin, whereby the resist film surface can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[8] Solvent The solvent that can be used in preparing the composition is not particularly limited as long as it can dissolve each component. For example, alkylene glycol monoalkyl ether carboxylate (such as propylene glycol monomethyl ether acetate), alkylene Glycol monoalkyl ether (such as propylene glycol monomethyl ether), alkyl lactate ester (such as ethyl lactate and methyl lactate), cyclic lactone (such as γ-butyrolactone, preferably 4 to 10 carbon atoms), chain or cyclic ketone (2- Heptanone, cyclohexanone, etc., preferably 4 to 10 carbon atoms, alkylene carbonate (ethylene carbonate, propylene carbonate, etc.), alkyl carboxylate (preferably alkyl acetate such as butyl acetate), alkoxy And alkyl acetate (ethyl ethoxypropionate) and the like. Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

  Of the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.

  These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40.

  The solvent having a hydroxyl group is preferably an alkylene glycol monoalkyl ether, and the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate.

[9] Other components In addition to the components described above, the composition of the present invention includes a carboxylic acid onium salt, a dissolution inhibiting compound having a molecular weight of 3000 or less, as described in Proceeding of SPIE, 2724, 355 (1996), and acid growth. An agent, a dye, a plasticizer, a photosensitizer, a light absorber, and the like can be appropriately contained.

[Pattern formation method]
The pattern forming method of the present invention includes steps of exposing and developing a resist film.

  The resist film is formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention described above, and more specifically, is preferably formed on a substrate. In the pattern forming method of the present invention, the step of forming a film of a resist composition on the substrate, the step of exposing the film, and the developing step can be performed by generally known methods.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used at a film thickness of 30 to 250 nm, more preferably at a film thickness of 30 to 200 nm, from the viewpoint of improving resolution. preferable. By setting the solid content concentration in the actinic ray-sensitive or radiation-sensitive resin composition to an appropriate range to have an appropriate viscosity, and improving the coating property and film forming property, such a film thickness is obtained. Can do.

  The total solid concentration in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is generally 1 to 10% by mass, more preferably 1 to 8.0% by mass, and still more preferably 1.0 to 6.0% by mass.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is used by dissolving the above components in a solvent, filtering the solution, and applying the solution to a support. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 microns or less, more preferably 0.05 microns or less, and still more preferably 0.03 microns or less. Note that a plurality of types of filters may be connected in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration.

  The composition of the present invention can be applied on a substrate (eg, silicon / silicon dioxide coating) used in the manufacture of integrated circuit elements by a suitable application method such as a spinner. Thereafter, it can be dried to form a photosensitive resist film.

  The resist film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common.

  It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.

  It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.

  The heating temperature is preferably 70 to 140 ° C for both PB and PEB, and more preferably 80 to 135 ° C.

  The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.

  Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

  The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

  Although it does not specifically limit as actinic light or a radiation, For example, they are a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), EUV light (13 nm), an electron beam etc., ArF excimer laser, EUV light, and an electron beam are preferable.

  As the alkaline developer in the development step, a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH) is usually used. In addition, inorganic alkali, primary to tertiary amine, alcohol amine, cyclic amine are also used. An alkaline aqueous solution such as can also be used.

  Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline developer.

  The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.

  The pH of the alkali developer is usually from 10.0 to 15.0.

  As the rinsing liquid, pure water is preferable, and an appropriate amount of a surfactant can be added and used.

  Note that an antireflection film may be applied in advance on the substrate before the photosensitive resist film is formed.

  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. 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.

  For a resist film comprising the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a liquid (immersion medium) having a refractive index higher than that of air between the film and the lens when irradiated with actinic rays or radiation. You may satisfy | fill and perform exposure (immersion exposure). Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.

  The immersion liquid used for the immersion exposure will be described below.

  The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the resist film. Is an ArF excimer laser (wavelength; 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-mentioned viewpoints.

  Further, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, the surface tension of the water is decreased and the surface activity is increased, so that the resist film on the wafer is not dissolved and the influence on the optical coating on the lower surface of the lens element can be ignored. An additive (liquid) may be added in a small proportion. The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specifically includes methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained. On the other hand, when an opaque material or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light, the optical image projected on the resist film is distorted. . Further, pure water filtered through an ion exchange filter or the like may be used.

  The electrical resistance of water is desirably 18.3 MQcm or more, the TOC (organic substance concentration) is desirably 20 ppb or less, and deaeration treatment is desirably performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

  As described above, when the film made of the composition of the present invention is exposed through an immersion medium, a hydrophobic resin (HR) can be further added as necessary.

  An immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) may be provided between the film of the composition of the present invention and the immersion liquid so that the film does not directly contact the immersion liquid. Good. The functions necessary for the top coat are suitability for application to the upper layer of the resist, transparency to radiation, particularly 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the upper layer of the resist.

  From the viewpoint of 193 nm transparency, the top coat is preferably a polymer that does not contain abundant aromatics. Specifically, the polymer contains a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, and silicon. Examples thereof include a polymer and a fluorine-containing polymer. The aforementioned hydrophobic resin (HR) is also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

  When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. In terms of being able to perform the peeling process simultaneously with the film development process, it is preferable that the peeling process can be performed with an alkaline developer. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the film.

  The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. In the case of using water as the immersion liquid in an ArF excimer laser (wavelength: 193 nm), the top coat for ArF immersion exposure is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.

  The topcoat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Further, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

  The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.

  The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by this.
[Synthesis Example 1: Synthesis of Compound Aa-1]

<< Synthesis of Intermediate 1 >>
In a 300 ml three-necked flask, 24.8 g (0.2 mol) of toluenethiol, 43.6 g (0.2 mol) of 4-iodotoluene, 3.8 g (0.02 mol) of copper iodide, 6.4 g of tetra n-butylammonium bromide ( 0.02 mol), 16 g (0.4 mol) of sodium hydroxide and 100 ml of toluene were added, and the mixture was stirred for 18 hours while heating under reflux in a nitrogen atmosphere. Thereafter, 500 ml of water was added to the reaction solution, extracted with 200 ml of ethyl acetate, dehydrated by adding magnesium sulfate, and filtered, and the resulting residue was concentrated under reduced pressure. Thereafter, the target product was separated by column chromatography (SiO ₂ , hexane), and the obtained residue was concentrated under reduced pressure. Then, it recrystallized with 50 ml of methanol, and 21.5g (yield: 50.2%) of intermediate bodies 1 were obtained.

¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 2.31 (6H, s), 7.07-7.09 (4H, s), 7.21-7.24 (4H, s).

<< Synthesis of Intermediate 2 >>
Compound (X) was dissolved in 25 g of methyl ethyl ketone, and 4.2 g of α-bromo-γ-lactone was added. After homogeneous dissolution, 4.7 g of potassium carbonate was added and stirred at 80 ° C. for 4 hours. After cooling to room temperature, 45 g of distilled water was added and stirred for 15 minutes, then added to 170 g of 1N aqueous hydrochloric acid, stirred at room temperature for 1 hour, and filtered to obtain 11.4 g of Intermediate 2.

<< Synthesis of Aa-1 >>
To a 50 ml eggplant flask, 1.54 g (7.19 mmol) of intermediate 1, 1.69 g (9.34 mmol) of ethyl 2-bromopropionate, 1.68 g (8.62 mmol) of silver boron tetrafluoride and 5 ml of chloroform were added. The mixture was stirred for 19 hours with heating under reflux. Thereafter, 9 g of Intermediate 2 was dissolved in a mixture of 50 g of acetonitrile and 20 g of water, stirred at room temperature for 1 hour, 40 g of methylene chloride was added, and the organic layer was washed 4 times with distilled water. Then, 6.2g of compounds (Aa-1) were obtained by depressurizingly distilling the solvent of an organic layer.

¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 1.16 (2H, d), 2.28 (1H, m), 2.35 (1H, m), 2.45 (6H, s), 2.62 (2H, m), 2.85 (2H, m), 3.46 (2H, m), 3.65 (1H, m), 3.68 (1H, m), 4.21 (1H) M), 4.41 (1H, m), 5.34 (2H, s), 4.98 (1H, m), 7.50 (4H, d), 8.05 (4H, d).

  The same operations as in Synthesis Example 1 were performed to synthesize compounds (Aa-2) to (Aa-18) shown below.

[Synthesis Example 2 Synthesis of Resin c]
Under a nitrogen stream, 25.5 g of cyclohexanone was placed in a three-necked flask and heated to 85 ° C. To this, the following compounds (monomer) were added in order from the left: 1.24 g, 4.58 g, 1.18 g, 3.19 g, 1.97 g, polymerization initiator V-601 (manufactured by Wako Pure Chemicals, 0.743 g), 46 g of cyclohexanone. The solution dissolved in was added dropwise over 6 hours. After completion of dropping, the reaction was further continued at 85 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixed solution of 420 g of hexane / 180 g of ethyl acetate over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 8.8 g of a resin d. The polymer composition ratio determined from NMR was 10/30/10/35/15. The weight average molecular weight (Mw) of the obtained resin d was 7900 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.52.

  The same operations as in Synthesis Example 2 were performed to synthesize resins a to c and e to g shown below as acid-decomposable resins (B).

<Resist preparation>
The components shown in Tables 2 and 3 below are dissolved in a solvent, and a solution with a solid content of 4% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.05 μm. Alternatively, a radiation sensitive resin composition was prepared. The actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in Tables 2 and 3.

<Resist evaluation>
(Exposure condition 1: ArF immersion exposure)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied and baked at 130 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. For this, an ArF excimer laser immersion scanner (SMTL XT1700i, NA 1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection) is used. The exposure was performed through a square array halftone mask having a pitch of 75 nm. Ultra pure water was used as the immersion liquid. Then, it heated at 105 degreeC for 60 second (PEB: Post Exposure Bake). Next, the film was developed with an aqueous tetramethylammonium hydroxide solution (2.38% by mass) for 30 seconds, rinsed with pure water, and then spin-dried to obtain a hole pattern.

(Exposure condition 2: ArF dry exposure)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied and baked at 130 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. For this, an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, σo / σi = 0.89 / 0.65) is used, and the hole portion is 75 nm and the pitch between holes is 90 nm. Exposure was through a square array of halftone masks. Thereafter, the mixture was heated at 100 ° C. for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsed with pure water, and spin-dried to obtain a hole pattern.

(CDU evaluation) [Local pattern dimension uniformity (Local CDU, nm)]
In one shot exposed at the optimum exposure amount in the exposure latitude evaluation, arbitrary 25 holes (that is, a total of 500 holes) are measured for each area in 20 areas each having an interval of 1 μm. These standard deviations were obtained and 3σ was calculated. The smaller the value, the smaller the dimensional variation, indicating better performance.

(Roundness evaluation) [(Roundness, nm)]
In one shot exposed at the optimal exposure amount in exposure latitude evaluation, 20 holes with a distance of 1 μm between each other, and an arbitrary 25 holes (that is, a total of 500 holes) are approximated to a perfect circle. Measurement was performed in the mode, and the radius of the hole pattern was measured at 32 points per hole. The variation (3σ) between the hole radius obtained by measurement and the radius when approximated to a perfect circle was calculated, the average value of these was calculated, and the roundness was calculated. The smaller the value, the closer to a perfect circle, indicating better performance.

  Abbreviations in the table represent the following.

[Compound (A)]

[Comparative Compound (A ′)]

[Acid generator]

[Resin (B)]

[Hydrophobic resin HR]

[Basic compounds]
DIA: 2,6-diisopropylaniline TEA: triethanolamine DBA: N, N-dibutylaniline PBI: 2-phenylbenzimidazole PEA: N-phenyldiethanolamine [a low molecular compound having a group capable of leaving by the action of an acid (D (Compound (D))]

[Surfactant]
W-1: Megafuck F176 (manufactured by DIC Corporation) (fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation) (fluorine and silicon)
W-3: PF6320 (manufactured by OMNOVA Solutions Inc.) (fluorine-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
〔solvent〕
S1: Propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane)
S2: 2-Heptanone S3: Cyclohexanone S4: γ-Butyrolactone S5: Propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol)
S6: Ethyl lactate S7: Propylene carbonate As is apparent from Table 2 and Table 3 above, the use of the compound (A) of the present invention improves the performance of CDU and roundness.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be suitably used in a lithography process in the production of electronic devices such as various semiconductor elements and recording media.

Claims (14)

An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (A) represented by the following general formula (1) and a resin (B) whose solubility in an alkaline developer is increased by the action of an acid.

In general formula (1),
R ₁ and R ₂ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. However, at least one of R ₁ and R ₂ is an aryl group, and R ₁ and R ₂ may be connected to each other to form a condensed ring.
R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R ₃ and R ₄ may be connected to each other to form a ring.
R ₅ represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group or an aralkyl group. R ₅ may be bonded to R ₃ or R ₄ to form a ring.
Q ⁻ represents —W ₁ N ⁻ W ₂ R _f or —SO ₃ ⁻ . Here, R _f represents an alkyl group, a cycloalkyl group, or an aryl group, and W ₁ and W ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or —N (R _x ) R _y —. Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x is may form a ring with R _y, may form a ring with R _N.
R _N represents an organic group containing at least one basic nitrogen atom. Q in the general formula (1) ^- is _-W 1 ^-N - _-W is 2 -R _f, sensitive or radiation-sensitive resin composition of claim 1. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein R ₅ in the general formula (1) is an alkoxy group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein R ₁ and R ₂ in the general formula (1) are both aryl groups.   Furthermore, the actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-4 containing hydrophobic resin (HR).   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5, wherein the hydrophobic resin (HR) is a hydrophobic resin having at least one of a fluorine atom and a silicon atom.   The actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-6 in which resin (B) contains the repeating unit which has a lactone structure or a sultone structure.   Furthermore, it contains a compound (C) that generates an acid upon irradiation with actinic rays or radiation, and the structure of the cation moiety of the compound (C) is the same as the structure of the cation moiety of the compound (A). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of 1 to 7.   The actinic-ray sensitive or radiation sensitive resin composition of Claim 8 whose content rate of the said compound (C) is 0.1-30 mass% on the basis of the total solid of a composition.   An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9.   The pattern formation method including the process of exposing the actinic-ray-sensitive or radiation-sensitive film of Claim 10, and developing the said exposed actinic-ray-sensitive or radiation-sensitive film.   The pattern formation method according to claim 11, wherein the exposure is immersion exposure.   The manufacturing method of an electronic device containing the pattern formation method of Claim 11 or 12.   An electronic device manufactured by the method for manufacturing an electronic device according to claim 13.