JP5887300B2 - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film and pattern forming method using the composition, and method for producing electronic device - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon reaction with actinic rays or radiation, an actinic ray-sensitive or radiation-sensitive film formed using the composition, and the The present invention relates to a pattern forming method using a composition, an electronic device manufacturing method, and an electronic device. More specifically, the present invention relates to an actinic ray used for a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, a further photofabrication process, a lithographic printing plate, and an acid curable composition. The present invention relates to a photosensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film formed using the composition, a pattern forming method using the composition, a method for manufacturing an electronic device, 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. A pattern is formed, which is a better system than the conventional naphthoquinone diazide / 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 compound having an aromatic group exhibits a large absorption in the 193 nm region. It wasn't. For this reason, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed.

  However, from the viewpoint of overall performance as a resist, it is extremely difficult to find an appropriate combination of resin, photoacid generator, basic compound, additive, solvent, etc. to be used, and it cannot be said that it is still sufficient. Is the actual situation. For example, it is desired to develop a resist that has less pattern collapse, is excellent in pattern roughness characteristics such as exposure latitude and line width roughness (LWR), and has little performance fluctuation with time.

Under such circumstances, various compounds have been developed for photoacid generators, which are the main constituents of chemically amplified resist compositions. In general, high acid generation efficiency is desired for photoacid generators, but high acid generation efficiency means that the photoacid generator is easily decomposed, and is a trade-off relationship between storage stability and storage stability. There are many cases. For this reason, it is a very difficult subject to achieve both high acid generation efficiency and storage stability.
For example, Patent Document 1 describes a photoacid generator of a naphthylsulfonium salt, but it cannot be said that it has sufficient performance in acid generation efficiency and storage stability, and further performance improvement is required. It has been.

  Further, since a large amount of photoacid generator is contained in the chemically amplified resist composition, the basic performance such as pattern collapse, exposure latitude, and LWR is greatly affected. For example, Patent Documents 2 and 3 disclose photoacid generators of phenylsulfonium salts in order to improve exposure latitude or focus margin in a resist composition, but the basic performance such as exposure latitude is sufficient. I can't say that. Satisfying all of these properties and storage stability is an important issue in the development of photoacid generators for photoresists.

JP 2004-59882 A JP 2012-31145 A JP 2012-97074 A

  An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that has little pattern collapse, has excellent pattern roughness characteristics such as exposure latitude and LWR, and has little fluctuation in performance over time, in view of the background art described above. The present invention provides an actinic ray-sensitive or radiation-sensitive film and a pattern forming method using the same, an electronic device manufacturing method, and an electronic device.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

That is, this invention has the following structures in one aspect | mode.
[1] An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound represented by the following general formula (1).

In the formula, A represents a divalent or trivalent hetero atom.
R _{1 to} R ₅ each independently represents a hydrogen atom or a substituent. Any two substituents represented by R _{1 to} R ₅ may be connected to each other to form a condensed ring together with the benzene ring in the formula.
R ₆ and R ₇ each independently represent an alkylene group, and R ₈ and R ₉ each independently represent a substituent.
Q represents a linking group containing a hetero atom.

s represents 1 when A is a divalent hetero atom, and represents 2 when A is a trivalent hetero atom. When s is 2, two R _{5 s} may be the same as or different from each other.

n and m each independently represents an integer of 0 to 12. When n is 2 or more, the plurality of R ₈ may be the same or different from each other, and the plurality of R ₈ may be connected to each other to form a non-aromatic ring together with R ₆ . When m is 2 or more, the plurality of R ₉ may be the same or different from each other, and the plurality of R ₉ may be connected to each other to form a non-aromatic ring together with R ₇ .

X ⁻ represents a non-nucleophilic anion.

[2] Q in the general formula (1) is the following group:

(Wherein R ₁₀ represents a hydrogen atom or a substituent; p represents an integer of 0 to 2), and is any linking group selected from [1]. A light-sensitive or radiation-sensitive resin composition.

[3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein X ⁻ in the general formula (1) is represented by the general formula (2).

In the general formula (2), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R _a and R _b each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R _a and R _b , each is the same But it can be different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents an organic group containing a cyclic structure.
x represents an integer of 1 to 20. y represents an integer of 0 to 10. z represents an integer of 0 to 10.

  [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], further comprising a resin that is decomposed by the action of an acid to increase the solubility in an alkali developer. object.

  [5] The sensation according to any one of [1] to [4], further comprising a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, or a basic compound. Actinic ray-sensitive or radiation-sensitive resin composition.

  [6] 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 [5].

[7] A pattern forming method comprising exposing the actinic ray-sensitive or radiation-sensitive film according to [6], and developing the exposed film.
[8] The pattern forming method as described in [7], wherein the exposure method is immersion exposure.

[9] An electronic device manufacturing method including the pattern forming method according to [7] or [8].
[10] An electronic device manufactured by the method for manufacturing an electronic device according to [9].
[11] A compound represented by the following general formula (5).

In the formula, A represents a divalent or trivalent hetero atom.
R _{1 to} R ₅ each independently represents a hydrogen atom or a substituent. Any two substituents represented by R _{1 to} R ₅ may be connected to each other to form a condensed ring together with the benzene ring in the formula.

R ₆ and R ₇ each independently represent an alkylene group, and R ₈ and R ₉ each independently represent a substituent.

Q ₁ is the following group:

(In the formula, R ₁₀ represents a hydrogen atom or a substituent. P represents an integer of 0 to 2).
s represents 1 when A is a divalent hetero atom, and represents 2 when A is a trivalent hetero atom. When s is 2, two R _{5 s} may be the same as or different from each other.

n and m each independently represents an integer of 0 to 12. When n is 2 or more, the plurality of R ₈ may be the same or different from each other, and the plurality of R ₈ may be connected to each other to form a non-aromatic ring together with R ₆ . When m is 2 or more, the plurality of R ₉ may be the same or different from each other, and the plurality of R ₉ may be connected to each other to form a non-aromatic ring together with R ₇ .
X ⁻ represents a non-nucleophilic anion.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes what does not have a substituent and what has 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).

  “Actinic ray” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, deep ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams (EB). ing. In the present invention, “light” means actinic rays or radiation.

  In addition, “exposure” in the present specification is not limited to exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams, unless otherwise specified. It also means drawing with. The actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be suitably used particularly for an ArF immersion exposure process.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises (A) a compound (hereinafter referred to as “compound (A)) that generates an acid upon irradiation with an actinic ray or radiation represented by the general formula (1) described later. Or “acid generator (A)”).

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention can improve pattern collapse by containing the compound (A). The compound (A) has a ring structure containing a heteroatom, and is considered to contribute to the improvement of pattern collapse by improving the adhesion between the pattern and the substrate by interaction with the substrate.

Further, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can improve exposure latitude and pattern roughness (LWR) by containing the compound (A). The reason for this is not clear, but compound (A) has a large amount of acid generated after exposure because light absorption and C—S ⁺ bond cleavage after excitation occur with high efficiency. Are evenly distributed. This is considered to contribute to the improvement of LWR. In addition, since compound (A) has a ring structure containing a heteroatom and an aromatic ring to which the heteroatom is connected, diffusion of compound (A) is suppressed by interaction with the resin in the resist. This is considered to contribute to the improvement of exposure latitude.

  Furthermore, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can suppress fluctuations in performance over time by containing the compound (A).

The reason for this is not clear, but in compound (A), there is always a highly polar heteroatom in Q around the sulfur atom of the sulfonium cation, and the affinity with the hydrophobic component in the resist is inhibited. Therefore, it is considered that the nucleophilic addition decomposition is less likely to occur, and the fluctuation in performance over time can be suppressed.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is, for example, a resin composition containing a resin having a group that is decomposed by the action of an acid or a resin composition containing a resin having a crosslinkable group. Is a resin composition containing a resin having a group that decomposes under the action of an acid. Hereinafter, each component of this composition is demonstrated.

[1] Compound (A) represented by general formula (1)
As described above, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains the compound (A) represented by the following general formula (1). The compound (A) is a compound that generates an acid upon irradiation with actinic rays or radiation.
Hereinafter, the compound (A) will be described in detail.

In general formula (1),
A represents a divalent or trivalent hetero atom.
R _{1 to} R ₅ each independently represents a hydrogen atom or a substituent. Any two substituents represented by R _{1 to} R ₅ may be connected to each other to form a condensed ring together with the benzene ring in the formula.

R ₆ and R ₇ each independently represent an alkylene group, and R ₈ and R ₉ each independently represent a substituent.
Q represents a linking group containing a hetero atom.
s represents 1 when A is a divalent hetero atom, and represents 2 when A is a trivalent hetero atom. When s is 2, two R _{5 s} may be the same as or different from each other.
n and m each independently represents an integer of 0 to 12. When n is 2 or more, the plurality of R ₈ may be the same or different from each other, and the plurality of R ₈ may be connected to each other to form a non-aromatic ring together with R ₆ . When m is 2 or more, the plurality of R ₉ may be the same or different from each other, and the plurality of R ₉ may be connected to each other to form a non-aromatic ring together with R ₇ .
X ⁻ represents a non-nucleophilic anion.

The general formula (1) will be described in detail.
A represents a divalent or trivalent hetero atom as described above, preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom or a nitrogen atom.

R < ₁ > -R < ₄ > represents a hydrogen atom or a substituent each independently as above-mentioned. Examples of the substituent include a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, nitrogen in the alkyl chain. Specifically, it may have an atom such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n -A linear alkyl group such as tetradecyl group and n-octadecyl group, and a branched alkyl group such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group, etc.), cycloalkyl group ( Preferably, it is a C3-C20 cycloalkyl group, and may have an oxygen atom or a sulfur atom in the ring, specifically, a cyclopropyl group, cyclopentyl. , A cyclohexyl group, a norbornyl group, an adamantyl group, etc.), 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 an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms such as phenyl or naphthyl), a heterocyclic group (preferably having 1 to 32 carbon atoms, More preferably, it is a heterocyclic group having 1 to 18 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazole. -1-yl), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms. Methylsilyl, 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, t-butoxy, dodecyloxy and the like; for example, cycloalkyloxy groups such as cyclopentyloxy and cyclohexyloxy), aryloxy A group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenoxy or 1-naphthoxy), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, more preferably carbon A heterocyclic oxy group of 1 to 18, for example, 1 -Phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy),
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, for example, alkyloxycarbonyloxy groups such as ethoxycarbonyloxy and t-butoxycarbonyloxy; cycloalkyloxycarbonyloxy groups such as cyclohexyloxycarbonyloxy group), aryloxy Sicarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonyloxy), carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably Is a carbamoyloxy group having 1 to 24 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy group (Preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (Preferably 1 to 38 carbon atoms, more preferably charcoal In alkylsulfonyloxy group having 1 to 24, for example, 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).

R _{1 to} R ₄ may further have a substituent. Examples of the substituent that R _{1 to} R ₄ may have include, for example, a halogen atom such as a fluorine atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, an alkyl group (preferably having 1 to 6 carbon atoms), a cyclo An alkyl group (preferably 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 20 carbon atoms), an acyloxy group (Preferably having 2 to 10 carbon atoms), alkoxycarbonyl group (preferably having 2 to 20 carbon atoms), aminoacyl group (preferably having 2 to 10 carbon atoms), and the like. The cycloalkyl group, aryl group, alkoxy group, and alkoxycarbonyl group as a substituent may be substituted with a halogen atom such as a fluorine atom. The cyclic structure such as an aryl group or a cycloalkyl group may be further substituted with an alkyl group (preferably having 1 to 10 carbon atoms). The aminoacyl group may be further substituted with an alkyl group (preferably having 1 to 10 carbon atoms).

The substituent represented by R _{1 to} R ₄ is preferably a linear or branched alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amino group, or an alkoxycarbonylamino group.

More preferably, the substituent represented by R _{1 to} R ₄ includes a linear or branched alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, or an alkoxycarbonylamino group.

More preferred examples of the substituent represented by R _{1 to} R ₄ include a linear or branched alkyl group, a cycloalkyl group, and an alkoxy group.

R ₅ represents a hydrogen atom or a substituent as described above. Examples of the substituent include the same as those described above as examples of the substituents R ₁ to R _4. Preferable examples of the substituent R ₅ include those similar to the specific examples and preferable examples illustrated as the alkyl group, cycloalkyl group, alkenyl group, aryl group and acyl group in the above-described substituents R _{1 to} R ₄ . . The substituent represented by R ₅ may further have a substituent, and examples of the substituent include specific examples similar to the specific examples described above as substituents that R _{1 to} R ₄ may further have. Can be mentioned.

In R _{1 to} R ₅ , any two substituents may be connected to each other to form a condensed ring together with the benzene ring in the formula. The two substituents 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, alkenyl group, —O—, —S—, —S (═O) —, —S (═O) ₂ —, —CO—, —N (R) — (wherein R represents a hydrogen atom, an alkyl group, an alkylcarbonyl group, or an alkyloxycarbonyl group), or a divalent linking group in which a plurality of these are combined is exemplified.

The condensed ring formed by R ₅ together with any of R _{1 to} R ₄ together with the benzene ring in the formula is a heterocyclic aromatic ring containing a heteroatom represented by A in the formula. The heterocyclic aromatic ring preferably has, for example, 6 to 20 carbon atoms. Specific examples include an acridine group, a xanthene group, a carbazole group, an indole group, a benzopyran group, a benzothiazole group, a benzoxazole group, Benzofuran group, dihydrobenzofuran group, benzothiophene group, dihydrobenzothiophene group, chroman group, thiochroman group, benzodioxane group, dibenzodioxin group, phenoxathiin group, dibenzo-1,4-dithiane group, phenothiazine group, dibenzothiophene group Etc.

As the condensed ring formed by connecting any two substituents of R _{1 to} R ₄ together with the benzene ring in the formula, a polycyclic aromatic hydrocarbon ring having 10 to 20 carbon atoms, or 6 to 6 carbon atoms Twenty polycyclic heteroaromatic rings are preferred. Specific examples of the polycyclic aromatic hydrocarbon group include naphthyl group, azulenyl group, acenaphthylenyl group, phenanthrenyl group, penalenyl group, phenanthracenyl group, fluorenyl group, anthracenyl group, pyrenyl group, benzopyrenyl group, biphenyl group and the like. Can be mentioned. Specific examples of the polycyclic heterocyclic aromatic group include the same specific examples as the specific examples of the heterocyclic aromatic ring.

R ₆ and R ₇ each independently represent an alkylene group, preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably an alkylene group having 2 to 3 carbon atoms. And most preferably an ethylene group.

R ₆ and R ₇ may have substituents R ₈ and R ₉ , respectively. Examples of the substituents R ₈ and R ₉ include the substituents described above as the substituents represented by R _{1 to} R ₅ . R ₈ and R ₉ preferably have an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. And an aryl group which may be used.

The alkyl group as R ₈ and R ₉ 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.

The cycloalkyl group as R ₈ and R ₉ 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 ₈ and R ₉ 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 ₈ and R ₉ is preferably an alkenyl group having 2 to 20 carbon atoms, and specifically has a double bond at any position of the alkyl group as R ₈ and R ₉ described above. Groups.

The substituent that may be possessed by these groups, for example, the same specific examples as the specific examples described above as substituent R ₁ to R ₄ may have further the like.

As described above, n and m each independently represent an integer of 0 to 12, and when n is 2 or more, a plurality of R ₄ may be the same or different from each other, and m is 2 or more. In this case, a plurality of R ₅ may be the same as or different from each other. n and m are preferably integers of 0 to 3.

As described above, when n is 2 or more, a plurality of R ₈ may be connected to each other to form a non-aromatic ring together with R ₆ , and preferably a 5-membered or 6-membered ring as the non-aromatic ring. And particularly preferably a 6-membered ring.

Further, as described above, when m is 2 or more, a plurality of R ₉ may be connected to each other to form a non-aromatic ring together with R ₇ , and preferably a 5-membered or 6-membered non-aromatic ring. And particularly preferably a 6-membered ring.

Q represents a linking group containing a hetero atom as described above, and is preferably any linking group selected from the following group (G).

In the formula, R ₁₀ represents a hydrogen atom or a substituent. p represents an integer of 0 to 2.
Examples of R ₁₀ as a substituent include the same groups as R _{1 to} R ₄ described above.
In one embodiment of the present invention, the linking group represented by Q is preferably —O—.

The substituent represented by R ₁₀ is preferably a group that reduces the basicity of the nitrogen atom. Specific examples include groups having electron withdrawing properties such as acyl groups and sulfonate groups. Examples of the acyl group include formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, and cyclohexanoyl group. Examples of the sulfonate group include a methane sulfonate group, an ethane sulfonate group, a propane sulfonate group, a butane sulfonate group, a paratoluene sulfonate group, and a trifluoromethane sulfonate group.

In one embodiment of the present invention, the compound (A) is preferably represented by the following general formula (5).

In the formula, Q ₁ represents any linking group selected from the above group (G). R _{1 to} R ₉ , A, X ⁻ , n, m and s have the same meanings as those in General Formula (1) above.

In one embodiment of the present invention, the compound (A) is preferably represented by the following general formula (1a).

In the formula, A represents a divalent or trivalent hetero atom.
Ra represents a hydrogen atom or a substituent.
Rb represents a substituent.
R ₆ and R ₇ each independently represent an alkylene group, and R ₈ and R ₉ each independently represent a substituent.
Q represents a linking group containing a hetero atom.
s represents 1 when A is a divalent hetero atom, and represents 2 when A is a trivalent hetero atom. When s is 2, two Ras may be the same or different from each other.
o represents an integer of 0-6. When o is 2 or more, the plurality of Rb may be the same as or different from each other.
n and m each independently represents an integer of 0 to 12. When n is 2 or more, the plurality of R ₈ may be the same or different from each other, and the plurality of R ₈ may be connected to each other to form a non-aromatic ring together with R ₆ . When m is 2 or more, the plurality of R ₉ may be the same or different from each other, and the plurality of R ₉ may be connected to each other to form a non-aromatic ring together with R ₇ .
X ⁻ represents a non-nucleophilic anion.

A, R ₆ , R ₇ , R ₈ , R ₉ , Q and X ⁻ in the formula have the same meanings as those in the general formula (1) above. As the substituent represented by Ra and Rb, the same specific examples as the substituents represented by R ₁ to R ₄ in the general formula, supra (1).

Examples of the non-nucleophilic anion represented by X ⁻ in the general formula (1) include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion. Etc. A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

Examples of the sulfonate anion include an alkyl sulfonate anion, an aryl sulfonate anion, and a camphor sulfonate anion.
Examples of the carboxylate anion include an alkylcarboxylate anion, an arylcarboxylate anion, and an aralkylcarboxylate anion.

  The alkyl group in the alkylsulfonate anion is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a pentyl group. , Neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclo Examples thereof include a propyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a boronyl group.

  The aryl group in the aryl sulfonate 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 and aryl group in the alkyl sulfonate anion and aryl sulfonate anion may have a substituent.
Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an alkylthio group.

  Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

  As the alkyl group, for example, preferably an alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl it can.

  As an alkoxy group, Preferably a C1-C5 alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. can be mentioned, for example.

  As the alkylthio group, for example, preferably an alkylthio group having 1 to 15 carbon atoms, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, pentylthio group. Group, neopentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, tridecylthio group, tetradecylthio group, pentadecylthio group, hexadecylthio group, heptadecylthio group, octadecylthio group , Nonadecylthio group, eicosylthio group and the like. The alkyl group, alkoxy group, and alkylthio group may be further substituted with a halogen atom (preferably a fluorine atom).

Examples of the alkyl group in the alkylcarboxylate anion include the same alkyl groups as in the alkylsulfonate anion.
Examples of the aryl group in the arylcarboxylate anion include the same aryl groups as in the arylsulfonate anion.
The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylmethyl group.

The alkyl group, aryl group and aralkyl group in the alkylcarboxylate anion, arylcarboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent are the same as those in the arylsulfonate anion. A halogen atom, an alkyl group, an alkoxy group, an alkylthio group, etc. can be mentioned.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. These alkyl groups may have a substituent, and examples of the substituent include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, and the like, which are substituted with a fluorine atom. Alkyl groups are preferred.

  Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

X ^- non-nucleophilic anion, alkanesulfonic acid anion position α is substituted with a fluorine atom of the sulfonic acid, a fluorine atom or a fluorine atom is substituted by a aryl sulfonate anion, an alkyl group is a fluorine atom A bis (alkylsulfonyl) imide anion substituted with a tris (alkylsulfonyl) methide anion in which an alkyl group is substituted with a fluorine atom is preferred. As the non-nucleophilic anion for X ⁻ , a perfluoroalkanesulfonic acid anion, a nonafluorobutanesulfonic acid anion, and a perfluorooctanesulfonic acid anion having 1 to 8 carbon atoms are particularly preferable.

In one embodiment of the present invention, the non-nucleophilic anion X ⁻ is preferably represented by the general formula (2). In this case, since the volume of the generated acid is large and the diffusion of the acid is suppressed, it is presumed that the improvement of the exposure latitude is further promoted.

In the general formula (2), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R _a and R _b each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R _a and R _b , each is the same But it can be different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.

A represents an organic group containing a cyclic structure.
x represents an integer of 1 to 20. y represents an integer of 0 to 10. z represents an integer of 0 to 10.

The anion of the general formula (2) will be described in more detail.
Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group in the alkyl group substituted with a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 4 carbon atoms is more preferable. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF _{3 , CH 2 CH 2 CF 3,} CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9, CH 2 CH ₂ C ₄ F ₉ is mentioned, among which fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

R _a and R _b represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group substituted with at least one fluorine atom of R _a and R _b include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , and C ₆ F _13. , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ Examples thereof include C ₃ F ₇ , CH ₂ C ₄ F ₉ , and CH ₂ CH ₂ C ₄ F ₉ , among which CF ₃ is preferable.

L represents a divalent linking group, and represents —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, —N (Ri) — (wherein Ri represents a hydrogen atom or alkyl), an alkylene group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group or an ethyl group, most preferably a methyl group. ), A cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), or a divalent linking group in which a plurality of these are combined. , —CO—, —SO ₂ —, —CON (Ri) —, —SO ₂ N (Ri) —, —CON (Ri) -alkylene group—, —N (Ri) CO-alkylene group—, —COO— Alkylene group- or -OCO-alkylene group- Preferably _there, -SO 2 -, - COO -, - OCO -, - COO- alkylene group -, - more preferably - OCO- alkylene group. The alkylene group in -CON (Ri) -alkylene group-, -N (Ri) CO-alkylene group-, -COO-alkylene group-, and -OCO-alkylene group- is preferably an alkylene group having 1 to 20 carbon atoms. An alkylene group having 1 to 10 carbon atoms is more preferable. When there are a plurality of L, they may be the same or different.

Specific examples and preferred examples of the alkyl group for Ri include those similar to the specific examples and preferred examples described above as R _{1 to} R ₄ in the general formula (1).

  The organic group containing the cyclic structure of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having an aromatic attribute but also aromaticity). For example, a tetrahydropyran ring, a lactone ring structure, and a sultone ring structure).

  The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a norbornene-yl group, or a tricyclodecanyl group (for example, tricyclo [ 5.2.1.0 (2,6)] decanyl group), tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group and the like are preferable, and an adamantyl group is particularly preferable. Also preferred are nitrogen atom-containing alicyclic groups such as piperidine group, decahydroquinoline group, decahydroisoquinoline group. Among them, an alicyclic group having a bulky structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, a decahydroquinoline group, and a decahydroisoquinoline group. And diffusibility in the film in the PEB (post-exposure heating) step can be suppressed, which is preferable from the viewpoint of improving exposure latitude. Of these, an adamantyl group and a decahydroisoquinoline group are particularly preferable.

  Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Of these, naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm.

Examples of the heterocyclic group include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, a furan ring, a thiophene ring, and a pyridine ring are preferable. Other preferred heterocyclic groups include the structures shown below (wherein X represents a methylene group or an oxygen atom, and R represents a monovalent organic group).

  The cyclic organic group may have a substituent, and as the substituent, an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), aryl Examples include a group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group.

  Note that the carbon constituting the organic group containing a cyclic structure (carbon contributing to ring formation) may be a carbonyl carbon.

  x is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. y is preferably 0 to 4, more preferably 0 or 1, and still more preferably 1. z is preferably 0 to 8, more preferably 0 to 4, and still more preferably 1.

In another embodiment of the present invention, the non-nucleophilic anion X ⁻ may be a disulfonylimide acid anion.

  The disulfonylimidoanion is preferably a bis (alkylsulfonyl) imide anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion is preferably an alkyl group having 1 to 5 carbon atoms.

  Two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms), and may form a ring together with the imide group and the two sulfonyl groups. The ring structure that may be formed by the bis (alkylsulfonyl) imide anion is preferably a 5- to 7-membered ring, and more preferably a 6-membered ring.

  These alkyl groups and alkylene groups formed by connecting two alkyl groups to each other can have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryl Examples thereof include an oxysulfonyl group and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

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

The compound (A) may be a compound having a plurality of structures represented by the general formula (1). For example, a compound having a structure in which R ₅ in general formula (1) is bonded to R ₅ in another general formula (1) through a single bond or a linking group may be used.

The compound represented by the general formula (1) or the general formula (1a) is represented by (total mass of all fluorine atoms contained in the compound) / (total mass of all atoms contained in the compound). The fluorine content is preferably 0.25 or less, more preferably 0.20 or less, still more preferably 0.15 or less, and particularly preferably 0.10 or less.

Although the preferable specific example of the compound (A) represented by the said General formula (1) is given below, this invention is not limited to these.

A method for synthesizing the compound (A) will be described.
The sulfonate anion or a salt thereof in the general formula (1) can be used for the synthesis of the compound (A) represented by the general formula (1). The sulfonate anion or its salt (for example, onium salt, metal salt) in the general formula (1) that can be used for the synthesis of the compound (A) can be obtained by using a general sulfonate esterification reaction or sulfonamidation reaction. Can be synthesized. For example, after selectively reacting one sulfonyl halide portion of a bissulfonyl halide compound with an amine, alcohol, or amide compound to form a sulfonamide bond, a sulfonic acid ester bond, or a sulfonimide bond, It can be obtained by a method of hydrolyzing a sulfonyl halide moiety or a method of opening a cyclic sulfonic anhydride with an amine, alcohol or amide compound.

Examples of the salt of the sulfonic acid anion in the general formula (1) include a metal salt of sulfonic acid and an onium salt of sulfonic acid. Examples of the metal in the metal salt of sulfonic acid include Na ⁺ , Li ⁺ and K ⁺ . Examples of the onium cation in the sulfonic acid onium salt include an ammonium cation, a sulfonium cation, an iodonium cation, a phosphonium cation, and a diazonium cation.

  Compound (A) can be synthesized by a method in which the sulfonate anion represented by the general formula (1) is subjected to salt exchange with a photoactive onium salt such as a sulfonium salt corresponding to the sulfonium cation in the general formula (1).

  In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, the compound (A) can be used alone or in combination of two or more. The content of the compound (A) in the composition of the present invention is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, still more preferably, based on the total solid content of the composition. 5 to 25% by mass.

The compound (A) may be used in combination with an acid generator other than the compound (A) (hereinafter also referred to as compound (A ′) or acid generator (A ′)).
Although it does not specifically limit as a compound (A '), Preferably the compound represented by the following general formula (ZI'), (ZII '), (ZIII') can be mentioned.

In the 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).

Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include a corresponding group in the compound (ZI′-1) described later.

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 different from at least one of R _{201 to} R ₂₀₃ of the other compound represented by the general formula (ZI ′). It may be a compound having a structure bonded through a bond or 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.

  Two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms), and may form a ring together with the imide group and the two sulfonyl groups.

  The alkylene group formed by linking two alkyl groups in these alkyl groups and bis (alkylsulfonyl) imide anions may have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group. Group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group, and the like, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferable.

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 aliphatic sulfonate anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a group having a fluorine atom or a fluorine atom, an alkyl group with a fluorine atom A substituted bis (alkylsulfonyl) imide anion and a tris (alkylsulfonyl) methide anion 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.

  As a more preferred (ZI ′) component, a compound (ZI′-1) described below can be exemplified.

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

Arylsulfonium _compound, all of R 201 _{to R 203} may be an aryl group _{or a} part of R 201 _{to R 203} is an aryl group, but the remainder is an alkyl group or a cycloalkyl _group, the R 201 _{to R 203} All are preferably aryl groups.

  Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an aryldicycloalkylsulfonium compound, and a triarylsulfonium compound is preferable. .

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms). , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, general formulas (ZII ′) and (ZIII ′) will be described.
In the 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 described as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI′-1). It is.

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Also as this substituent, what the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the above-mentioned compound (ZI′-1) may have may be mentioned.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} the general formula (ZI ′).
Examples of the acid generator (A ′) that can be used in combination with the acid generator in the present invention 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 are the same as the specific examples of the aryl group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI′-1). Can be mentioned.

Specific examples of the alkyl group and the cycloalkyl group represented by R ₂₀₈ , R _209, and R ₂₁₀ include an alkyl group and a cycloalkyl group represented by R ₂₀₁ , R _202, and R ₂₀₃ in the general formula (ZI′-1), respectively. The thing similar to a specific example 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 to 2 carbon atoms. 12 alkenylene groups (for example, ethenylene 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.) Can be mentioned.
Among acid generators that can be used in combination with the acid generator of the present invention, particularly preferred examples are given below.

  The usage-amount of the acid generator at the time of using a compound (A) and a compound (A ') together is 99/1-20/80 by mass ratio (compound (A) / compound (A')). It is preferably 99/1 to 40/60, more preferably 99/1 to 50/50. When the compound (A) and the compound (A ′) are used in combination, a combination in which the anion portion of the compound (A) and the anion portion of the compound (A ′) are the same is preferable.

[2] Resin that is decomposed by the action of an acid to increase the solubility in an alkali developer The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is decomposed by the action of an acid to increase the solubility in an alkali developer. Resin (hereinafter also referred to as “acid-decomposable resin” or “resin (B)”) may be contained.

  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 obtained by substituting the hydrogen atom of these alkali-soluble groups 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 or an alkyl group which may have a substituent.
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 alkyl group which may have a substituent represented by Xa ₁ include a group represented by a methyl group or —CH ₂ —R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom) hydroxyl group or a monovalent organic group, and examples thereof 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. An alkyl group, more preferably a methyl group. In one embodiment, Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.

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 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, an adamantyl group A polycyclic cycloalkyl group such as a group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

The cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group It may be replaced with.

The repeating unit represented by the general formula (AI) preferably has, for example, 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.

  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 20 to 80 mol%, more preferably 25 to 75 mol%, based on all repeating units in the resin (B), 30 More preferably, it is -70 mol%.

  Although the specific example of the repeating unit which has a preferable 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 them, each is independent. p represents 0 or a positive integer. Examples of the substituent containing a polar group represented by Z include a linear or branched alkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group, and a cycloalkyl group. Is an alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.

The resin (B) preferably contains, for example, a repeating unit represented by the general formula (3) as the repeating unit represented by the general formula (AI).

In general formula (3),
R ₃₁ represents a hydrogen atom or an alkyl group.
R ₃₂ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group.
R ₃₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R ₃₂ is bonded. In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.

The alkyl group for R ₃₁ may have a substituent, and examples of the substituent include a fluorine atom and a hydroxyl group.

R ₃₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₃₂ is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group.

The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably a 3- to 8-membered ring, and more preferably a 5- or 6-membered ring.

In the monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom, examples of the hetero atom that can form the ring include an oxygen atom and a sulfur atom. Examples of the group having a hetero atom include a carbonyl group and the like. Can be mentioned. However, the group having a hetero atom is preferably not an ester group (ester bond).

The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably formed only from the carbon atom and the hydrogen atom.

The repeating unit represented by the general formula (3) is preferably a repeating unit represented by the following general formula (3 ′).

In general formula (3 ′), R ₃₁ and R ₃₂ have the same meanings as in general formula (3).

Although the specific example of the repeating unit which has a structure represented by General formula (3) is given below, it is not limited to these.

  The content of the repeating unit having the structure represented by the general formula (3) is preferably 20 to 80 mol% with respect to all repeating units in the resin (B), and preferably 25 to 75 mol%. Is more preferable, and it is still more preferable that it is 30-70 mol%.

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

In formulas (I) and (II),
R ₁ and R ₃ each independently represent a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₁₁ . R ₁₁ represents 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 the carbon atom to which R ₂ is bonded.

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 ₁₁ are the same as those described for R ₁₁ 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 an alkyl group having 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.

  Examples of the substituent that each of the above groups may have include the same groups as those described above as the substituent that each of the groups in the general formula (AI) may have.

  The acid-decomposable resin is a resin containing a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferred.

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. When two or more types of repeating units of general formula (I) are included, the repeating unit in which the alicyclic structure formed by R together with the carbon atom is a monocyclic alicyclic structure, and the alicyclic structure formed by R together with the carbon atom are It is preferable that both the repeating unit which is a polycyclic alicyclic structure is included. The monocyclic alicyclic structure preferably has 5 to 8 carbon atoms, more preferably 5 or 6 carbon atoms, and particularly preferably 5 carbon atoms. As the polycyclic alicyclic structure, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable.

One type of repeating unit having an acid-decomposable group contained in the resin (B) may be used, or two or more types may be used in combination. The following combinations are preferred when used in combination. In the following formula, each R independently represents a hydrogen atom or a methyl group.

  In one embodiment, the resin (B) preferably contains a repeating unit having a cyclic carbonate structure. This cyclic carbonate structure is a structure having a ring including a bond represented by —O—C (═O) —O— as an atomic group constituting the ring. The ring containing a bond represented by —O—C (═O) —O— as the atomic group constituting the ring is preferably a 5- to 7-membered ring, and most preferably a 5-membered ring. Such a ring may be condensed with another ring to form a condensed ring.

  The resin (B) preferably contains a repeating unit having a lactone structure or a sultone (cyclic sulfonate ester) structure.

Any lactone group or sultone group can be used as long as it has a lactone structure or a sultone structure, but it is preferably a 5- to 7-membered lactone structure or a sultone structure, and a 5- to 7-membered lactone A structure in which another ring structure is condensed to form a bicyclo structure or a spiro structure in the structure or sultone structure is preferable. 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 or sultone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), and more preferably (LC1-4). By using a specific lactone structure or sultone structure, LWR and development defects 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. .

The resin (B) preferably contains a repeating unit having a lactone structure or a sultone structure represented by the following general formula (III).

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 .
Z is independently a single bond, an ether bond, an ester bond, an amide bond, or a urethane bond when there are a plurality of Z.

Or urea bond

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

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
n _is the repetition number of the structure represented in -R 0 -Z-, an integer of 0-2.
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, alkoxy group such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group, and acetoxy group such as acetyloxy group and propionyloxy 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. A preferable cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. 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 monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure, and the general formula (LC1-1) described above as a specific example A lactone structure or a sultone structure represented by ~ (LC1-17), (SL1-1) and (SL1-2) is exemplified, and a 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.

  In general formula (III), it is preferable that n is 1 or 2.

  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.
In the following formulae, Me represents a methyl group.

As the repeating unit having a lactone structure or a sultone structure, 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 are as defined 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 ′ are the number of substituents and each independently 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, particularly preferably at the α-position.

Specific examples of the group having a lactone structure represented by the general formula (III-1) or (III-1 ′) or the repeating unit having a sultone structure 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.

  The content of the repeating unit represented by the general formula (III) is preferably 15 to 60 mol%, more preferably 20 to 60 mol in total with respect to all repeating units in the resin (B) when plural types are contained. %, More preferably 30 to 50 mol%.

  Resin (B) may also contain a repeating unit having the above-mentioned lactone structure or sultone structure in addition to the unit represented by formula (III).

Specific examples of the repeating unit having a lactone group or a sultone group include the following in addition to the specific examples given above, but the present invention is not limited thereto.

Among the specific examples, particularly preferred repeating units include the following repeating units. By selecting an optimal lactone group or sultone group, the pattern profile and the density dependency are improved.

  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.

  The content of the repeating unit having a lactone structure or a sultone structure other than the repeating unit represented by the general formula (III) is 15 to 60 mol% in total with respect to all the repeating units in the resin when a plurality of types are contained. More preferably, it is 20-50 mol%, More preferably, it is 30-50 mol%.

  In order to enhance the effect of the present invention, two or more kinds of lactone or sultone repeating units selected from general formula (III) can be used in combination. When using together, it is preferable to select and use 2 or more types from the lactone or sultone repeating unit in which n is 1 in general formula (III).

The resin (B) preferably has a repeating unit having a hydroxyl group or a cyano group other than the general formulas (AI) and (III). 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 content 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 the 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. Preferred monocyclic hydrocarbon groups are monocyclic hydrocarbon groups having 3 to 7 carbon atoms, and more preferred 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 from 1 to 40 mol%, more preferably from 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 11,000. 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 55 to 95 mass%, based on the total solid content.
In addition, the resins of the present invention may be used alone or in combination.

[3] Basic Compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound in order to reduce a change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number) 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

  Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undec-7-ene etc. are mentioned. Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris ( and t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. As the compound having an onium carboxylate structure, an anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

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

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. As the halogen atom, chloride, bromide, and iodide are particularly preferable. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

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

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

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

It is preferable to have at least one oxyalkylene group between the sulfonate group and the nitrogen atom. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

The following compounds are also preferable as the basic compound.

  As basic compounds, in addition to the above-mentioned compounds, JP2011-22560A [0180] to [0225], JP2012-137735A [0218] to [0219], International Publication Pamphlet WO2011 / 158687A1 [ [0416] to [0438] can also be used. The basic compound may be a basic compound or an ammonium salt compound whose basicity is lowered by irradiation with actinic rays or radiation.

  These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

  The composition of the present invention may or may not contain a basic compound, but when it is contained, the content of the basic compound is based on the solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Usually, it is 0.001-10 mass%, Preferably it is 0.01-5 mass%.

  The use ratio of the acid generator (including the acid generator (A ′)) and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, 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 resolution from being reduced due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

  These basic compounds are preferably used in a molar ratio of low molecular compound (D) / basic compound = 100/0 to 10/90 with respect to low molecular compound (D) shown in the following item [4]. It is more preferable to use at 100/0 to 30/70, and it is particularly preferable to use at 100/0 to 50/50.

  The basic compound here does not include (C) a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, which will be described below.

  Further, an onium salt that is a weak acid relative to the acid generator can also be used as the basic compound.

  When an acid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the acid generator are mixed and used, the acid generated from the acid generator by irradiation with actinic rays or radiation When it collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

The onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ represents a hydrocarbon group which may have a substituent, and Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. Each of the M ⁺ is independently a sulfonium or iodonium cation.

Preferable examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cation exemplified for the acid generator (ZI) and the iodonium cation exemplified for (ZII).

  Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include the structure exemplified in paragraph [0198] of JP2012-242799A.

  Preferable examples of the anion moiety of the compound represented by the general formula (d1-2) include a structure exemplified in paragraph [0201] of JP2012-242799A.

  Preferable examples of the anion moiety of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.

  An onium salt that is a weak acid relative to an acid generator is a compound that has a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety are linked by a covalent bond. Good.

Such a compound is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

In general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
-X ^- it ^is, -COO _^-, -SO 3 _- represents an anion portion selected from ^{_{-R 4 -, -SO 2 -,}} -N. R ₄ has 1 having a carbonyl group: —C (═O) —, a sulfonyl group: —S (═O) ₂ —, and a sulfinyl group: —S (═O) — at the site of connection with the adjacent N atom. Represents a valent substituent.

R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In (C-3), two of R _{1 to} R ₃ may be combined to form a double bond with the N atom.

Examples of the substituent having 1 or more carbon atoms in R _{1 to} R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino. A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.

L ₁ as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L ₁ is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

  Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.

  Preferable examples of the compound represented by the general formula (C-2) include compounds exemplified in paragraphs [0012] to [0013] of JP 2012-189977 A.

  Preferable examples of the compound represented by the general formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.

  The content of the onium salt that is a weak acid relative to the acid generator is preferably 0.5 to 10.0% by mass, and preferably 0.5 to 8.0% by mass based on the solid content of the composition. % Is more preferable, and 1.0 to 8.0% by mass is even more preferable.

[4] A low molecular 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 compound having a nitrogen atom and having a group leaving by the action of an acid (hereinafter referred to as “compound”). (C) ") may also be contained.

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

Compound (C) 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 each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group ( Preferably it represents C1-C10) or an alkoxyalkyl group (preferably C1-C10). Rb may be connected 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). ), For example, groups derived from linear or branched alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., derived from these alkanes Groups substituted with one or more cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, etc., cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane Derived from cycloalkanes Groups derived from these cycloalkanes are, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t- Groups derived from aromatic compounds such as benzene, naphthalene and anthracene, groups derived from these aromatic compounds, groups substituted with one or more linear or branched alkyl groups such as butyl groups For example, a linear or branched group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, or a t-butyl group. Groups substituted with one or more alkyl groups, pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquino A group derived from a heterocyclic compound such as benzene, indazole, benzimidazole, etc., or a group derived from these heterocyclic compounds, one or more or one group derived from a linear, branched alkyl group or aromatic compound One or more or one group derived from an aromatic compound such as a phenyl group, a naphthyl group, or an anthracenyl group as a group substituted above, a group derived from a linear or branched alkane, or a group derived from a cycloalkane Examples include groups substituted by the above, or groups in which the above substituent is substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo 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 connecting 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.

It is particularly preferable that the compound (C) has a structure represented by the following general formula (6).

  In the general formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.

  Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.

l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.

  In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are described above as the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as 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.

  In addition, the heterocyclic ring formed by connecting the Ra to each other preferably has 20 or less carbon atoms. 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, indole, indoline, 1,2, , 4-tetrahydroquinoxaline, perhydroquinoline, groups derived from heterocyclic compounds such as 1,5,9-triazacyclododecane, and groups derived from these heterocyclic compounds are linear or branched alkanes Groups derived from the above, groups derived from cycloalkanes, groups derived from aromatic compounds, groups derived from heterocyclic compounds, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups, etc. Examples include groups substituted with one or more functional groups or one or more functional groups.

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

  The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.

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

  The content of the compound (C) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 0.001 to 20% by mass, more preferably based on the total solid content of the composition. It is 0.001-10 mass%, More preferably, it is 0.01-5 mass%.

[5] Hydrophobic resin (HR)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention, particularly when applied to immersion exposure, is a hydrophobic resin having at least one of a fluorine atom and a silicon atom (hereinafter referred to as “hydrophobic resin (HR)”). May also be included). 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 the 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 formulas (C-Ia) to (C-Id), R ₁₀ and R ₁₁ 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.

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 formulas (C-II) and (C-III), 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 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 to increase 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 ″), a side chain having at least one group selected from the group consisting of the above (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-pinel 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 an adamantyl group, a noradamantyl group, a decalin group, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a 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. , Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, Aralkyl groups such as benzyl, phenethyl and cumyl groups, aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanyl groups, acyl groups such as valeryl groups, acyloxy groups such as butyryloxy groups, vinyl groups, propenyls 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),
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.
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 .
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). If R ₄ is a plurality may be the same or different, and two or more R ₄ are attached, may 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-attracting 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 is bonded to the main chain of the resin 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 connected 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.
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

  Examples of the repeating unit (bz) having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin include the same repeating units having an acid-decomposable group as mentioned for the resin (B).

  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 formulas (CIII) and (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 (CIII) and (BII-AB) are shown below, but the present invention is not limited to these. 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 repeating units in each resin (the positional relationship of each repeating unit in each resin shown in the specific example corresponds to the positional relationship of the composition ratio numbers in Table 1), weight average Indicates molecular weight and 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 is not necessary.

  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 BLO defect performance are improved.

  When the hydrophobic resin has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the 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 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.

[6] Resin (D) which is substantially different from the resin (B) and contains substantially no fluorine atom or silicon atom
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is different from the resin (B) in that it contains substantially no fluorine atom and no silicon atom (D) (hereinafter simply referred to as “resin (D)”. May also be contained in an amount of 0.1% by weight or more and less than 10% by weight based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.

  Here, the resin (D) does not substantially contain a fluorine atom or a silicon atom. Specifically, the content of the repeating unit having a fluorine atom or a silicon atom is included in all the repeating units in the resin (D). It is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, and ideally 0 mol%, that is, fluorine atoms and silicon atoms. Does not contain.

  In the composition of the resin (D) in the present invention, the resin (D) is unevenly distributed in the surface layer portion of the resist film, is excellent in local pattern dimension uniformity and EL, and achieves reduction of water residue defects. Content is 0.1 mass% or more and less than 10 mass% on the basis of the total solid in the said actinic-ray-sensitive or radiation-sensitive resin composition, 0.2-8 mass% is preferable, 0 3 to 6% by mass is more preferable, and 0.5 to 5% by mass is particularly preferable.

In the present invention, the mass content of the CH ₃ partial structure of the side chain portion in the resin (D) in the resin (D) is 12.0% or more, and 18.0% or more. Is preferred. Thereby, a low surface free energy can be achieved, the resin (D) can be unevenly distributed on the surface layer portion of the resist film, and as a result, local pattern dimension uniformity (in forming a fine hole pattern) Is excellent in the uniformity of the hole diameter) and EL, and in immersion exposure, it is possible to achieve reduction of residual water defects.

Incidentally, the upper limit of the mass content of CH ₃ partial structure contained in the side chain moiety in the resin (D) is preferably at most 50.0%, more preferably 40% or less.

Here, the methyl group directly bonded to the main chain of the resin (D) (for example, α-methyl group of a repeating unit having a methacrylic acid structure) is unevenly distributed on the surface of the resin (D) due to the influence of the main chain. Therefore, it is not counted as not included in the CH ₃ partial structure in the present invention. More specifically, the resin (D) includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In this case, when R _{11 to} R ₁₄ are CH ₃ “as is”, the CH ₃ is not included (not counted) in the CH ₃ partial structure of the side chain moiety in the present invention.

Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone counts as CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), the CH ₃ partial structure in the present invention is counted as having “one”.

In the general formula (M),
R < ₁₁ > -R < ₁₄ > represents a side chain part each independently.
Examples of R _{11 to} R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.
Examples of the monovalent organic group for R _{11 to} R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, arylaminocarbonyl group and the like.
The monovalent organic group may further have a substituent, and as the substituent, specific examples described later as the substituent that the aromatic group Ar ₂₁ in the general formula (II) may have, The thing similar to a preferable example is mentioned.

In the present invention, the CH ₃ partial structure possessed by the side chain moiety in the resin (D) (hereinafter also simply referred to as “side chain CH ₃ partial structure”) includes the CH ₃ partial structure possessed by an ethyl group, a propyl group, or the like. Is included.

Hereinafter, the mass content of the CH ₃ partial structure of the side chain portion in the resin (D) in the resin (D) (hereinafter simply referred to as “mass content of the side chain CH ₃ partial structure in the resin (D)”. Rate ").

Here, the mass content of the side chain CH ₃ partial structure in the resin (D) is such that the resin (D) is composed of repeating units D1, D2, ..., Dx, ..., Dn, and the repeating units D1, D2, .., Dx,..., Dn in the resin (D) will be described as an example where the molar fractions in the resin (D) are ω1, ω2,.

(1) First, the mass content (MCx) of the side chain CH ₃ partial structure of the repeating unit Dx is expressed as “100 × 15.03 × (number of CH ₃ partial structures in the side chain portion in the repeating unit Dx) / repeating The molecular weight (Mx) of the unit Dx ”can be calculated by the calculation formula.

Here, the number of CH ₃ partial structures in the side chain portion in the repeating unit Dx does not include the number of methyl groups directly connected to the main chain.

(2) Next, using the mass content of the calculated side chain CH ₃ partial structure repeating unit each, by the following equation, the mass content of the side chain CH ₃ partial structure in the resin (D) Can be calculated.

Mass content of side chain CH ₃ partial structure in resin (D):
DMC = Σ [(ω1 × MC1) + (ω2 × MC2) + ... + (ωx × MCx) + ... + (ωn × MCn)]
Specific examples of the mass content of the CH ₃ partial structure in the side chain portion of the repeating unit Dx are described below, but the present invention is not limited thereto.

Specific examples of the mass content of the side chain CH ₃ partial structure in the resin (D) will be described below, but the present invention is not limited thereto.

The resin (D) preferably has at least one repeating unit represented by the following general formula (V) or (VI), and at least one of the repeating units represented by the following general formula (V) or (VI). More preferably, it consists of only one.

In the general formula (V),
R _{21 to} R ₂₃ each independently represents a hydrogen atom or an alkyl group.
Ar ₂₁ represents an aromatic group. R ₂₂ and Ar ₂₁ may form a ring, in which case R ₂₂ represents an alkylene group.

In the general formula (VI),
R _{31 to} R ₃₃ each independently represents a hydrogen atom or an alkyl group.

X ₃₁ represents —O— or —NR ₃₅ —. R ₃₅ represents a hydrogen atom or an alkyl group.

R ₃₄ represents an alkyl group or a cycloalkyl group.

The alkyl group of R _{21 to} R ₂₃ in the general formula (V) is preferably an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group), more preferably a methyl group or an ethyl group, A methyl group is particularly preferred.

Examples of the alkylene group in the case where R ₂₂ and Ar ₂₁ form a ring include a methylene group and an ethylene group.

As R _{21 to} R ₂₃ in the general formula (V), a hydrogen atom or a methyl group is particularly preferable.

The aromatic group of Ar ₂₁ in the general formula (V) may have a substituent, an aryl group having 6 to 14 carbon atoms such as a phenyl group or a naphthyl group, or thiophene, furan, pyrrole, benzo Examples include aromatic groups containing heterocycles such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, etc. An aryl group that may be used is preferable.

Examples of the substituent that the aromatic group Ar ₂₁ may have include an alkyl group, an alkoxyl group, and an aryl group, but the mass content of the CH ₃ partial structure of the side chain portion in the resin (D) From the viewpoint of increasing the surface free energy and decreasing the surface free energy, an alkyl group and an alkoxyl group are preferable, an alkyl group having 1 to 4 carbon atoms and an alkoxyl group are more preferable, a methyl group, an isopropyl group, a tert-butyl group, and a tert-butoxy group. Is particularly preferred.
In addition, the aromatic group for Ar ₂₁ may have two or more substituents.

In the general formula (VI), the alkyl group of R _{31 to} R ₃₃ and R ₃₅ is preferably an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group), methyl group, ethyl group Are more preferable, and a methyl group is particularly preferable. As R < ₃₁ > -R < ₃₃ > in general formula (III), a hydrogen atom and a methyl group are especially preferable each independently.

X ₃₁ in the general formula (VI) is preferably —O— or —NH— (that is, R ₃₅ in —NR ₃₅ — is a hydrogen atom), particularly preferably —O—.

In the general formula (VI), the alkyl group for R ₃₄ may be either a chain or a branch, and a chain alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an n- Butyl group, n-hexyl group, n-octyl group, n-dodecyl group, etc.) and branched alkyl groups (for example, isopropyl group, isobutyl group, tert-butyl group, methylbutyl group, dimethylpentyl group, etc.). However, from the viewpoint of increasing the mass content of the CH ₃ partial structure of the side chain moiety in the resin (D) and decreasing the surface free energy, it is preferably a branched alkyl group having 3 to 10 carbon atoms. A branched alkyl group is more preferable, and a branched alkyl group having 3 to 8 carbon atoms is particularly preferable.

In the general formula (VI), the cycloalkyl group for R ₃₄ may have a substituent, and may be a monocyclic cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, a norbornyl group, a tetracyclodeca Examples thereof include polycyclic cycloalkyl groups such as an nyl group and an adamantyl group, but monocyclic cycloalkyl groups are preferable, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are more preferable, and cyclohexyl groups are particularly preferable.

Examples of the substituent that R ₃₄ may have include an alkyl group, an alkoxyl group, and an aryl group, but increases the mass content of the CH ₃ partial structure of the side chain portion in the resin (D). From the viewpoint of reducing the surface free energy, an alkyl group and an alkoxyl group are preferable, an alkyl group having 1 to 4 carbon atoms and an alkoxyl group are more preferable, and a methyl group, isopropyl group, tert-butyl group, and tert-butoxy group are particularly preferable. .

In addition, the cycloalkyl group for R ₃₄ may have two or more substituents.

R ₃₄ is preferably not a group capable of decomposing and leaving by the action of an acid, that is, the repeating unit represented by the general formula (VI) is preferably not a repeating unit having an acid-decomposable group.

In the general formula (VI), R ₃₄ is most preferably a branched alkyl group having 3 to 8 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a cyclohexyl group substituted with an alkoxyl group.

Specific examples of the repeating unit represented by formula (V) or (VI) are shown below, but the present invention is not limited thereto.

  When the resin (D) has a repeating unit represented by the general formula (V) or (VI), the content of the repeating unit represented by the general formula (V) or (VI) From the viewpoint of reducing the free energy and achieving the effect of the present invention, it is preferably in the range of 50 to 100 mol%, more preferably in the range of 65 to 100 mol% with respect to all repeating units in the resin (D). It is more preferable, and it is especially preferable that it is the range of 80-100 mol%.

  Resin (D) is further similar to those described above for resin (B), having a repeating unit having an acid-decomposable group, a repeating unit having a lactone structure, a repeating unit having a hydroxyl group or a cyano group, an acid group (alkali-soluble And a repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability may be included.

  Specific examples and preferred examples of each repeating unit that the resin (D) may have include the same specific examples and preferred examples of each repeating unit described above for the resin (B).

  However, from the viewpoint of achieving the effects of the present invention, it is more preferable that the resin (D) does not have a repeating unit having an acid-decomposable group, an alkali-soluble repeating unit, or a repeating unit having a lactone structure.

  The weight average molecular weight of the resin (D) according to the present invention is not particularly limited, but the weight average molecular weight is preferably in the range of 3000 to 100,000, more preferably in the range of 6000 to 70000, and preferably in the range of 10,000 to 40000. A range is particularly preferred. In particular, when the weight average molecular weight is in the range of 10,000 to 40,000, the formation of a fine hole pattern is excellent in local CDU and exposure latitude, and in immersion exposure, the defect performance is excellent. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

  The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50. The smaller the molecular weight distribution, the better the resolution and resist pattern shape.

  Resin (D) based on this invention can be used individually by 1 type or in combination of 2 or more types.

  As the resin (D), various commercially available products can be used, or they 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). However, in the synthesis of the resin (D), the reaction The concentration is preferably 10 to 50% by mass.
Specific examples of the resin (D) are shown below, but the present invention is not limited thereto.

[7] Surfactant The composition of the present invention may further contain a surfactant or may not contain a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.

  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 the total solid content of the composition. Preferably it is 0.0001-2 mass% with respect to a minute, More preferably, it is 0.0001-1 mass%, Most preferably, it is 0.0005-1 mass%.

  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 actinic ray-sensitive or radiation-sensitive resin composition according to the present invention usually further contains a solvent.

Examples of the solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and monoketone which may contain a ring. Examples include organic solvents such as compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

  Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate. And propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene Preferred is glycol monoethyl ether.

  Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

  Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, -Penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcyclo A preferred example is heptanone.

  Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.

  Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.

  Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

  As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid -2- (2-ethoxyethoxy) ethyl and propylene carbonate are mentioned.

  In the present invention, the above solvents may be used alone or in combination of two or more.

  In the present invention, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group may be used as the organic solvent.

  As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, propylene glycol monomethyl ether, More preferred is ethyl lactate. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate and 2-heptanone are most preferred.

  The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

  The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

[9] Dissolution-inhibiting compound having a molecular weight of 3000 or less, which decomposes by the action of an acid to increase the solubility in an alkali developer, and increases the solubility in an alkali developer by the action of an acid, having a molecular weight of 3000 or less As a dissolution inhibiting compound (hereinafter also referred to as “dissolution inhibiting compound”), Proceeding of SPIE, 2724, 355, since it does not lower the permeability of 220 nm or less.
An alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in (1996) is preferred. Examples of the acid-decomposable group and alicyclic structure are the same as those described above for the resin (B).

  When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, the phenolic hydroxyl group of the phenol compound is an acid-decomposable group as a dissolution inhibiting compound. Those containing a structure substituted with are preferred. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.

The addition amount of the dissolution inhibiting compound is preferably 0.5 to 50% by mass, more preferably 0.5 to 40% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive resin composition.
Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

[10] Other components In addition to the components described above, the composition of the present invention may appropriately contain a carboxylic acid onium salt, a dye, a plasticizer, a photosensitizer, a light absorber, and the like.

[11] Pattern Forming 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 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm 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 is applied by a suitable application method, such as a spinner, onto a substrate (eg, silicon / silicon dioxide coating) as used in the manufacture of integrated circuit devices. Thereafter, it can be dried to form a photosensitive resist film.

The 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 120 ° C., more preferably 80 to 110 ° C. for both PB and PEB.
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, ArF excimer laser, EUV light, an electron beam, etc., ArF excimer laser, EUV light, and an electron beam are preferable.

  The developer used in the step of developing the resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is not particularly limited. For example, a developer containing an alkali developer or an organic solvent. (Hereinafter also referred to as an organic developer) can be used. Alternatively, pattern formation may be performed by combining a development process using an alkaline developer and a development process using an organic developer. Examples of such a pattern forming method include a pattern forming method described in US Pat. No. 8,227,183.

  Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, fourth amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkaline aqueous solutions such as cyclic amines such as quaternary ammonium salts, pyrrole, and pihelidine can be used. Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution. 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 organic developer, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

  Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Examples include ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate. be able to.

  Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.

  Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.

  Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

  Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

  A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. The content of water contained in the organic developer is preferably less than 10% by mass, and more preferably contains substantially no water.

  That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.

  In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

An appropriate amount of a surfactant can be added to the organic developer as required.

  In addition, a basic compound can be added to the organic developer as necessary. As the basic compound, nitrogen-containing compounds such as the above-described amine compounds and ammonium salts can be preferably used.

  The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant. The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

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

  As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.

  Moreover, the process which removes the developing solution or rinse liquid adhering on a pattern with a supercritical fluid can be performed after a image development process or a rinse process.

Before forming the photosensitive film (resist film), an antireflection film may be coated on the substrate in advance.
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.

Exposure (immersion exposure) may be performed by filling a liquid (immersion medium) having a higher refractive index than air between the film and the lens during irradiation with actinic rays or radiation. Thereby, resolution can be improved. The immersion medium used is preferably water. Water is also suitable in terms of a small temperature coefficient of refractive index, ease of availability, and ease of handling.
A medium having a refractive index of 1.5 or more can also be used in that the refractive index can be improved. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, an additive for the purpose of improving the refractive index may be added in a small proportion. Examples of additives are described in detail in chapter 12 of the CM publication “Immersion Lithography Processes and Materials”. On the other hand, the presence of impurities that are opaque to 193 nm light and impurities whose refractive index is significantly different from that of water causes distortion of the optical image projected on the film, and therefore, distilled water is preferred as the water to be used. Further, pure water purified with an ion exchange filter or the like may be used. The electric resistance of pure 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.

  An immersion liquid poorly soluble film (hereinafter also referred to as “top coat”) may be provided between the resist film and the immersion liquid in order to avoid contact between the resist film and the immersion liquid. Functions necessary for the top coat include suitability for application on a resist film, transparency to radiation, particularly radiation having a wavelength of 193 nm, and poor immersion liquid solubility. As the top coat, it is preferable to use a top coat that can be uniformly coated on the resist film without being mixed with the resist film.

  From the viewpoint of transparency at 193 nm, the topcoat is preferably a polymer that does not contain aromatics. Examples of such polymers include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, and fluorine-containing polymers. The hydrophobic resin described above is also suitable as a top coat. When impurities are eluted from the top coat into the immersion liquid, the optical lens is contaminated. Therefore, 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 a small penetration into the resist film is preferable. It is preferable that the peeling process can be performed with an alkali developer in that the peeling process can be performed simultaneously with the resist development process. 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 resist.

  There is preferably no or small difference in refractive index between the top coat and the immersion liquid. In this case, the resolution can be improved. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water as the immersion liquid. Therefore, the top coat for ArF immersion exposure is close to the refractive index of water (1.44). preferable.

  Moreover, it is preferable that a topcoat is a thin film from a viewpoint of transparency and a refractive index. The top coat is preferably not mixed with the resist film and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used in the top coat is hardly soluble in the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and is not water-soluble. It is preferable that the medium be a sex medium. Further, when the immersion liquid is an organic solvent, the top coat 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, this invention is not limited to this.

[Synthesis Example 1: Synthesis of Compound A-35]
Compound A-35 was synthesized according to the following scheme.

<< Synthesis of A-35 '>>
To a three-necked flask was added 10 g (69.4 mmol) of 1-naphthol, 14.63 g (76.3 mmol) of 1-bromo-2-methoxyethane, 19.2 g (138.4 mmol) of potassium carbonate, and 50 g of DMAc, and the mixture was heated to 90 ° C. And stirred for 12 hours. Thereafter, 100 ml of water and 100 ml of ethyl acetate were added, the organic layer was separated, and washed successively with 100 ml of 0.5 M hydrochloric acid aqueous solution, 50 g of saturated aqueous sodium hydrogen carbonate, and 50 g of saturated aqueous sodium chloride. Then, 13.3g (65.9 mmol) of target compound A-35 'was obtained by concentrating an organic layer.

¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 3.51 (3H, s), 3.89 (2H, t), 4.30 (2H, t), 6.81 (1H, d), 7.56 (1H, t), 7.41-7.54 (3H, m), 7.76-7.81 (1H, m), 8.28-8.31 (1H, m)
<< Synthesis of A-35 >>
After adding 2 g (9.8 mmol) of A-35 ′ to a three-necked flask and dissolving it in 20 g of dichloromethane, 4.2 g (19.6 mmol) of trifluoroacetic anhydride and 1.15 g (11.8 mmol) of methanesulfonic acid were added. In addition, it was cooled to an internal temperature of 4 ° C. in an ice bath. Next, 1, 4
-A solution of 1.3 g (10.8 mmol) of thioxan-4-oxide in 5 g of dichloromethane was added dropwise to the reaction solution using a dropping funnel. During the dropping, the internal temperature was adjusted to 10 ° C. or lower. Further, after stirring for 1 hour at an internal temperature of 4 ° C., 20 g of water was added, 3.7 g (9.8 mmol) of sodium (adamantan-1-ylmethoxycarbonyl) -difluoro-methanesulfonate was added, and 1 hour at room temperature. Stir. The organic layer was separated, washed with 20 g of water, concentrated and crystallized to obtain 5.7 g (9.1 mmol) of the target compound A-35.

¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 1.52 (6H, brs), 1.56-1.69 (6H, m), 1.91 (3H, s), 3.49 (3H , S), 3.77-3.93 (8H, m), 4.22 (2H, ddd), 4.37 (2H, brt), 4.44 (2H, td), 7.15 (1H, d), 7.58 (1H, t), 7.74 (1H, t), 8.30-8.40 (3H, m)
Another compound (A) described in Table 2 below was synthesized by the same synthesis method as that for Compound A-35.

[Synthesis Example 2: Synthesis of Resin (3)]
Under a nitrogen stream, 11.5 g of cyclohexanone was placed in a three-necked flask and heated to 85 ° C. To this, 1.98 g, 3.05 g, 0.95 g, 2.19 g, 2.76 g, polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 0.453 g) were added cyclohexanone 21 in order from the left. A solution dissolved in 0.0 g 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 9.1 g of the following resin (3) which is an acid-decomposable resin. It was. The polymer composition ratio determined from NMR was 20/25/10/30/15. The weight average molecular weight of the obtained resin (3) was 10400 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.56.

  The same operations as in Synthesis Example 2 were performed to synthesize the following resins (1), (2), and (4) to (6) as acid-decomposable resins.

<Resist preparation>
The components shown in Table 2 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. Resin composition (positive resist composition) was prepared. The actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in Table 2.
About each component in Table 2, the ratio at the time of using multiple is a mass ratio.

  In Table 2, the actinic ray-sensitive or radiation-sensitive resin composition does not contain a hydrophobic resin (HR), and after forming a film, the top coat contains a hydrophobic resin (HR) as an upper layer. When a protective film was formed, the usage form was described as “TC”.

<Evaluation of resist using alkaline developer>
<Resist evaluation>
(Exposure condition 1: ArF immersion exposure)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a 12-inch 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. In the case of using a top coat, a 3% by mass solution obtained by further dissolving a resin for top coat in decane / octanol (mass ratio 9/1) is applied on the film obtained above, and at 85 ° C. for 60 seconds. Baking was performed to form a 50 nm thick top coat layer. An ArF excimer laser immersion scanner (XTML1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection, manufactured by ASML) was used, and a 1: 1 line and space with a line width of 48 nm. The pattern was exposed through a 6% halftone mask. Ultra pure water was used as the immersion liquid. After heating at 100 ° C. for 60 seconds, paddle development with tetramethylammonium hydroxide aqueous solution (2.38 mass%) for 30 seconds, paddle with pure water, rinse, spin dry, and resist pattern. Formed.

(Exposure condition 2: ArF dry exposure)
An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied on a 12-inch silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 75 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. An ArF excimer laser scanner (PAS5500 / 1100 manufactured by ASML, NA0.75, Dipole, σo / σi = 0.89 / 0.65) was used, and a 6% half of a 1: 1 line and space pattern with a line width of 75 nm was used. Exposed through tone mask. 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 resist pattern.

(Exposure latitude evaluation)
In exposure condition 1, the exposure amount that reproduces a line and space mask pattern with a line width of 48 nm is set as the optimal exposure amount, and when the exposure amount is changed, an exposure amount width that allows a pattern size of 48 nm ± 10% is obtained, This value was divided by the optimum exposure amount and displayed as a percentage. In exposure condition 2, the exposure amount that reproduces a line-and-space mask pattern with a line width of 75 nm is set as the optimal exposure amount, and when the exposure amount is changed, an exposure amount width that allows a pattern size of 75 nm ± 10% is obtained. This value was divided by the optimum exposure amount and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

(LWR evaluation)
The obtained line / space = 1/1 line pattern (ArF dry exposure: line width 75 nm, ArF immersion exposure: line width 48 nm) was observed with a scanning microscope (S9380 manufactured by Hitachi, Ltd.), and the longitudinal direction of the line pattern In the range of 2 μm of the edge, the line width was measured at 50 points, the standard deviation was obtained for the measurement variation, and 3σ was calculated. A smaller value indicates better performance.

(Pattern collapse evaluation)
The exposure amount that reproduces the mask pattern of 48 nm line / 48 nm space in the exposure condition 1 and the exposure amount that reproduces the mask pattern of 75 nm line / 75 nm space in the exposure condition 2 is further increased from the optimal exposure amount. When the line width of the formed line pattern is narrowed, the line pattern is defined as the minimum line width that can be resolved without falling down. The smaller the value, the finer pattern is resolved without falling, and the pattern collapse is less likely to occur and the resolution is higher.

(Stability of resist over time)
The temporal stability of the resist was judged by a guarantee period during which the resist performance did not vary, and was evaluated by the following (1) contact angle temporal stability test and (2) line width temporal stability test.

[Line width stability test: exposure condition (1)]
Evaluation was made based on a line width difference between a resist that was aged for 30 days at 40 ° C., 50 ° C., and 60 ° C. and a resist that was aged for 30 days at 0 ° C. (reference resist).

Specifically, first, an exposure dose E ₁ for reproducing a mask pattern of 45 nm (line / space = 1/1) was obtained for a resist that was aged for 30 days at 0 ° C. Next, the three types of resist films heated for 30 days were exposed for E ₁ minute. The line width of the obtained pattern was measured with a scanning electron microscope (S9260 manufactured by Hitachi, Ltd.), and the variation value of the pattern line width with respect to the line width (45 nm) obtained with the reference resist was obtained.

  Based on the obtained three points of data, the X-axis represents the reciprocal of the temperature over time (degrees Celsius converted to Kelvin), and the Y-axis represents the line width fluctuation value per day (that is, the obtained line width fluctuation value is 30). The reciprocal of (the value divided by) was plotted on a semilogarithmic graph and approximated by a straight line. In the obtained straight line, the value of the Y coordinate in the X coordinate corresponding to the time-lapse temperature = 25 ° C. was read. The value of the read Y coordinate was defined as the number of days with a guaranteed line width of 1 nm under room temperature conditions (25 ° C.).

[Line width aging stability test: exposure condition (2)]
Evaluation was made based on a line width difference between a resist that was aged for 30 days at 40 ° C., 50 ° C., and 60 ° C. and a resist that was aged for 30 days at 0 ° C. (reference resist).

Specifically, first, an exposure amount E ₁ for reproducing a mask pattern of 75 nm (line / space = 1/1) was obtained for a resist that was aged for 30 days at 0 ° C. Next, the three types of resist films heated for 30 days were exposed for E ₁ minute. The line width of the obtained pattern was measured with a scanning electron microscope (S9260 manufactured by Hitachi, Ltd.), and the fluctuation value of the pattern line width with respect to the line width (75 nm) obtained with the reference resist was determined.

  Based on the three points of data obtained, the X-axis represents the reciprocal of the temperature over time (Celsius converted to Kelvin), and the Y-axis represents the line width fluctuation value per day (that is, the obtained line width fluctuation value). The inverse of (value divided by 30) was plotted on a semilogarithmic graph and approximated by a straight line. In the obtained straight line, the value of the Y coordinate in the X coordinate corresponding to the time-lapse temperature = 25 ° C. was read. The value of the read Y coordinate was defined as the number of days with a guaranteed line width of 1 nm under room temperature conditions (25 ° C.).

[Contact angle aging stability test: exposure conditions (1), (2)]
Similar to [Stability of line width with time: exposure conditions (1), (2)], the change with time of contact angle was evaluated and plotted, and the guaranteed number of days for 1 ° contact angle under room temperature conditions (25 ° C.) (= Reciprocal value of dynamic receding contact angle fluctuation value per day) was calculated. The contact angle was measured with a fully automatic contact angle meter (DropMaster 700 / Kyowa Interface Science) for the dynamic receding contact angle with pure water before exposure.

  Among the abbreviations in the table, the following were used among those shown in the specific examples.

<Compound (A)>

<Other acid generators>

<Resin (B)>
For each of the following resins, the composition ratio of the repeating units is a molar ratio.

<Basic compound>
DIA: 2,6-diisopropylaniline
TEA: Triethanolamine
DBA: N, N-dibutylaniline
PBI: 2-phenylbenzimidazole PEA: N-phenyldiethanolamine

[Low molecular compound (C) (compound (C)) having a group capable of leaving by the action of an acid]]

<Hydrophobic resin (HR)>
The hydrophobic resin (HR) was appropriately selected from the resins (B-1) to (B-56) listed above.

<Resin (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〕
A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: Cyclohexanone A3: γ-Butyrolactone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate As is clear from the results shown in Table 2, Comparative Examples 1 to 6 using an acid generator that does not satisfy the general formula (1) have small exposure latitude, large LWR, exposure latitude and LWR. You can see that both are inferior.

  On the other hand, in Examples 1 to 25 using the compound (A) satisfying the general formula (1) as an acid generator, the exposure latitude is large, the LWR is small, both the exposure latitude and the LWR are excellent, and the resist is stable over time. It turns out that it is excellent.

  The 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.

<Evaluation of resist using organic solvent developer>
[Synthesis Example 3: Synthesis of Resin (7)]
102.3 parts by mass of cyclohexanone was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, the monomer represented by the following structural formula M-1 22.2 parts by mass, the monomer represented by the following structural formula M-2 22.8 parts by mass, and represented by the following structural formula M-3. A mixed solution of 6.6 parts by mass of monomer, 189.9 parts by mass of cyclohexanone, dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] over 5 hours. It was dripped. After completion of dropping, the mixture was further stirred at 80 ° C. for 2 hours. The reaction solution is allowed to cool and then reprecipitated and filtered with a large amount of hexane / ethyl acetate (mass ratio 9: 1), and the resulting solid is vacuum-dried to obtain 41.1 mass of the resin (7) of the present invention. I got a part.

The obtained resin (7) had a weight average molecular weight (Mw: polystyrene equivalent) determined from GPC (carrier: tetrahydrofuran (THF)) of Mw = 9500, and the dispersity was Mw / Mn = 1.60. ^The composition ratio measured by ¹³ C-NMR was 40/50/10.

Resins (8) to (15) were synthesized in the same manner as in Synthesis Example 3. The synthesized polymer structure is described below.

The composition ratio (molar ratio; corresponding in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit are shown in the table below.

<Resist preparation>
The components shown in Table 4 below are dissolved in a solvent to prepare a solution having a solid content concentration of 3.8% by mass, and each is filtered through a polyethylene filter having a pore size of 0.03 μm. A composition (resist composition) was prepared.

<Resist evaluation>
(ArF immersion exposure)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto the silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. An actinic ray-sensitive or radiation-sensitive resin composition was applied thereon and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.

  The obtained wafer was used with an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) 1: Exposure was through a 6% halftone mask with a one line and space pattern. 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 by paddle with a negative developer (butyl acetate) for 30 seconds, and paddled with a rinse solution [methyl isobutyl carbinol (MIBC)] for 30 seconds for rinsing. Subsequently, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to form a 1: 1 line and space pattern with a line width of 48 nm.

Exposure latitude evaluation, LWR evaluation, collapse evaluation, and stability over time were evaluated in the same manner as the above evaluation methods. The evaluation results are shown in Table 4 below.

Claims (21)

An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound represented by the following general formula (1):

In the formula, A represents a divalent or trivalent hetero atom.
R _{1 to} R ₅ each independently represents a hydrogen atom or a substituent. Any two substituents represented by R _{1 to} R ₅ may be connected to each other to form a condensed ring together with the benzene ring in the formula.
R ₆ and R ₇ each independently represent an alkylene group, and R ₈ and R ₉ each independently represent a substituent.
Q represents a linking group containing a hetero atom.
s represents 1 when A is a divalent hetero atom, and represents 2 when A is a trivalent hetero atom. When s is 2, two R _{5 s} may be the same as or different from each other.
n and m each independently represents an integer of 0 to 12. When n is 2 or more, the plurality of R ₈ may be the same or different from each other, and the plurality of R ₈ may be connected to each other to form a non-aromatic ring together with R ₆ . When m is 2 or more, the plurality of R ₉ may be the same or different from each other, and the plurality of R ₉ may be connected to each other to form a non-aromatic ring together with R ₇ .
X ⁻ represents a non-nucleophilic anion. Q in the general formula (1) is the following group:

(Wherein R ₁₀ represents a hydrogen atom or a substituent; p represents an integer of 0 to 2). A light-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein Q in the general formula (1) is -O-. It is sensitive or radiation-sensitive resin composition according to any one of claims 1-3, characterized by being represented by the general formula (2) ^- X in the general formula (1).

In general formula (2), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R _a and R _b each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when a plurality of R _a and R _b are present, R _a and R _b are the same But it can be different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents an organic group containing a cyclic structure.
x represents an integer of 1 to 20. y represents an integer of 0 to 10. z represents an integer of 0 to 10. Furthermore, the actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-4 containing resin (B) which decomposes | disassembles by the effect | action of an acid and increases the solubility with respect to an alkali developing solution. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5, wherein the resin (B) is a resin containing a repeating unit represented by the general formula (I).

In general formula (I),
R ₁ Each independently represents a hydrogen atom, an optionally substituted methyl group or —CH. ₂ -R ₁₁ Represents a group represented by R ₁₁ Represents a monovalent organic group.
R ₂ Each independently represents an alkyl group or a cycloalkyl group.
R is R ₂ Represents an atomic group necessary for forming an alicyclic structure together with a carbon atom to which is bonded. R in general formula (I) ₂ Is an actinic ray-sensitive or radiation-sensitive resin composition according to claim 6, which is a branched alkyl group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 5 to 7, wherein the resin (B) is a resin containing a repeating unit represented by the general formula (II).

In general formula (II),
R ₃ Each independently represents a hydrogen atom, an optionally substituted methyl group or —CH. ₂ -R ₁₁ Represents a group represented by R ₁₁ Represents a monovalent organic group.
R ₄ , R ₅ And R ₆ Each independently represents an alkyl group or a cycloalkyl group. R in the general formula (II) ₄ , R ₅ And R ₆ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8, wherein at least one of the groups is a polycyclic cycloalkyl group. Furthermore, the actinic ray sensitivity or sensitivity according to any one of claims 1 to 9 , further comprising a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, or a basic compound. Radiation resin composition. The actinic-ray sensitive or radiation sensitive resin composition of Claim 10 which contains the onium salt which becomes a weak acid relatively with respect to an acid generator as said basic compound. Furthermore, the actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-11 containing hydrophobic resin. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 12, wherein the hydrophobic resin contains a fluorine atom or a silicon atom. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 12 or 13, wherein the content of the hydrophobic resin is 0.1 to 10% by mass based on the total solid content of the composition. Furthermore, the actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-14 containing resin (D) which does not contain a fluorine atom and a silicon atom substantially. CH which side chain part of said resin (D) has ₃ The actinic-ray sensitive or radiation sensitive resin composition of Claim 15 whose mass content rate which occupies in the said resin (D) of a partial structure is 12.0% or more. Any one actinic ray-sensitive or radiation-sensitive resin composition actinic ray-sensitive or radiation-sensitive film formed by using the according to claims 1-16. A pattern forming method comprising exposing the actinic ray-sensitive or radiation-sensitive film according to claim 17 and developing the exposed film. The pattern forming method according to claim 18 , wherein the exposure method is immersion exposure. The pattern forming method according to claim 18, wherein the developer used for the development is a developer containing an organic solvent. The manufacturing method of an electronic device containing the pattern formation method of any one of Claims 18-20 .