TWI627660B - Pattern forming method, method for manufacturing electronic device and electronic device, actinic-ray- or radiation-sensitive resin composition, and resist film - Google Patents

Abstract

The pattern forming method of the present invention comprises the steps of: forming a film using the photosensitive ray-sensitive or radiation-sensitive resin composition of the following (i) or (ii); exposing the film; and using an alkali developing The liquid or a developing solution containing an organic solvent removes the exposed portion of the exposed film to form a pattern.

(i) a sensitizing ray-sensitive or radiation-sensitive resin composition containing (A1) resin; (ii) a sensitizing ray-sensitive or radiation-sensitive resin containing (A2) resin and (AD) a compound having a monovalent iodine atom Composition.

Description

Pattern forming method, method of manufacturing electronic component, and electronic component, And a sensitizing ray-sensitive or radiation-sensitive resin composition and a resist film

The present invention relates to a microlithography process or other photolithography that can be preferably used in the fabrication of ultra-large scale integrated circuits (LSIs) or high-capacity microchips. a pattern forming method of a process, a method of manufacturing an electronic component, an electronic component, and a sensitizing ray-sensitive or radiation-sensitive resin composition and a resist film.

More specifically, the present invention relates to a pattern forming method and an electronic component which can be preferably used for microfabrication of a semiconductor element using an electron beam or Extreme Ultraviolet (EUV) light (wavelength: around 13 nm). A manufacturing method and an electronic component, and a sensitizing ray-sensitive or radiation-sensitive resin composition and a resist film.

In the past, in the manufacturing process of a semiconductor device such as an integrated circuit (IC) or an LSI, it has been composed by using a photoresist. The lithography of the object is used for microfabrication. In recent years, with the high integration of integrated circuits, it has been demanded to form ultrafine patterns of submicron regions or quarter micron regions. Along with this, the exposure wavelength also tends to be shorter than that of the KrF excimer laser light from the g-ray to the i-ray. Further, in addition to excimer laser light, lithography using electron beams or X-rays has been developed (see, for example, Patent Document 1 and Patent Document 2).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-72483

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-174894

In recent years, lithography using extreme ultraviolet rays (EUV light) has also been positioned as a next-generation or next-generation pattern forming technique, and it is desired to achieve high sensitivity and high resolution.

The present inventors have studied the resist compositions described in Patent Document 1 and Patent Document 2, and as a result, it has been found that the sensitivity and the resolution are insufficient.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a pattern forming method capable of achieving high sensitivity and high resolution, a method of manufacturing an electronic component using the same, an electronic component, and a sensitizing ray or a radiation sensitization A resin composition and a resist film using the same.

That is, the present invention provides the following [1] to [16].

[1] A pattern forming method comprising: a step of forming a film using a photosensitive ray-sensitive or radiation-sensitive resin composition of the following (i) or (ii); a step of exposing the film; and using a base a developing solution for removing the exposed portion of the exposed film to form a pattern, (i) a photosensitive ray-sensitive or radiation-sensitive resin composition containing the resin (A1), wherein the resin (A1) contains: a repeating unit which decomposes by an action of an acid to generate a polar group, and a repeating unit containing a partial structure which is not desorbed by actinic rays or radiation and has a monovalent iodine atom; (ii) contains a resin ( A2) a photosensitive ray-sensitive or radiation-sensitive resin composition of a compound (AD) having a monovalent iodine atom, wherein the resin (A2) contains a group having a polar group which is decomposed by an action of an acid to generate a polar group. Repeat unit.

[2] A pattern forming method comprising: a step of forming a film using the photosensitive ray-sensitive or radiation-sensitive resin composition of (i) or (ii); a step of exposing the film; and using The developing solution of the organic solvent removes the unexposed portion of the exposed film to form a pattern.

[3] The pattern forming method according to [1], wherein the sensitizing ray-sensitive or radiation-sensitive resin composition is the sensitized ray-sensitive or radiation-sensitive resin composition (i).

[4] The pattern forming method according to any one of [1] to [3] wherein the total solid content in the photosensitive ray-sensitive or radiation-sensitive resin composition (i) is based on The content of the resin (A1) is from 25% by mass to 99% by mass.

[5] The pattern forming method according to any one of [1] to [4] wherein the resin (A1) contains a repeating unit represented by the following formula (1'),

In the formula (1'), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; and R ₁₃ may also bond with Ar _{1 ;} to form a ring, in the case when R ₁₃ is bonded to Ar _1, R ₁₃ represents an alkylene group; X ₁ represents a single bond, alkylene, aromatic ring group, -O -, - S -, - CO -, - COO-, -SO ₂ NH-, -SO ₂ O-, -NR-, a divalent nitrogen-containing non-aromatic heterocyclic group, or a divalent linking group comprising a combination of these groups; R represents a hydrogen atom or An alkyl group; Ar ₁ represents an aromatic ring group; RI represents an iodine atom or an organic group containing at least one iodine atom; and n represents an integer of 1 or more.

[6] The pattern forming method according to [5], wherein RI in the formula (1') is an iodine atom.

[7] The pattern forming method according to [5] or [6], wherein n in the formula (1') is an integer of 2 or more.

[8] [5] to [7] The method of forming a pattern according to any one of claims, wherein in the general formula (1 ') is X ₁ is -COO-.

[9] The pattern forming method according to any one of [1] to [8] wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains an acid generated by irradiation with actinic rays or radiation. Compound (B).

[10] The pattern forming method according to any one of [3] to [8] wherein the resin (A1) contains a repeating unit having a group which generates an acid by irradiation with actinic rays or radiation.

[11] The pattern forming method according to any one of [1] to [10] wherein the exposure is exposure using EUV light.

[12] A method of producing an electronic component, comprising the pattern forming method according to any one of [1] to [11].

[13] An electronic component produced by the method of producing an electronic component according to [12].

[14] A photosensitive ray-sensitive or radiation-sensitive resin composition which is used in a pattern forming method and which is the above (i) or (ii), wherein the pattern forming method comprises: using sensitizing rayiness Or a step of forming a film by the radiation-sensitive resin composition; a step of exposing the film; and a step of removing the exposed portion of the exposed film using an alkali developer to form a pattern.

[15] A photosensitive ray-sensitive or radiation-sensitive resin composition which is used in a pattern forming method and which is the above (i) or (ii), wherein the pattern forming method comprises: using sensitizing rayiness Or a step of forming a film by the radiation-sensitive resin composition; a step of exposing the film; and a step of removing the unexposed portion of the exposed film using a developing solution containing an organic solvent to form a pattern.

[16] A resist film formed of the sensitized ray-sensitive or radiation-sensitive resin composition as described in [14] or [15].

According to the present invention, it is possible to provide a pattern forming method capable of achieving high sensitivity and high resolution, a method of manufacturing an electronic component using the same, an electronic component, and a sensitizing ray-sensitive or radiation-sensitive resin composition and an anti-resistant composition therewith Etch film.

Hereinafter, embodiments of the present invention will be described in detail.

In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the term "alkyl" means not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "light" as used in this specification refers not only to extreme ultraviolet rays (EUV light) but also to electron beams.

In addition, in this specification, "exposure" is not only an exposure using extreme ultraviolet rays (EUV light), but also an exposure by an electron beam, unless otherwise indicated.

The term "actinic ray" or "radiation" as used in the present specification means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, and an extreme ultraviolet ray (EUV light). X-rays, electron beams, etc. Further, the term "light" as used in the present invention means actinic ray or radiation. In addition, the term "exposure" as used in the present specification refers to exposure of far ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers, and the use of particle beams such as electron beams and ion beams, unless otherwise specified. The drawing is also included in the exposure.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is a sensitized ray-sensitive or radiation-sensitive resin composition of the following (i) or (ii) used in the pattern forming method to be described later.

(i) a photosensitive ray-sensitive or radiation-sensitive resin composition containing a resin containing a repeating unit having a group which generates a polar group by decomposition by an action of an acid, and containing no photochemical a repeating unit having a partial structure having a monovalent iodine atom by irradiation of radiation or radiation; (ii) a sensitizing ray-sensitive or radiation-sensitive resin containing a resin (A2) and a compound (AD) having a monovalent iodine atom And the resin (A2) contains a repeating unit having a group which generates a polar group by decomposition by an action of an acid.

According to the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention, high sensitivity and resolution can be achieved. Although the reason is uncertain, it can be estimated as follows.

First, when exposure is performed using EUV light, the resin composition absorbs light to generate electrons, and the generated electrons cause decomposition of the acid generator to generate an acid.

It is considered that at this time, the sensitized ray-sensitive or radiation-sensitive resin of the present invention Since the composition contains an iodine atom having a high absorption coefficient of EUV light, EUV light can be absorbed in a large amount, and high sensitivity is obtained.

In addition, in the case of exposure using an electron beam, the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention contains iodine atoms, so that a large amount of electrons are generated and high sensitivity is obtained.

Further, it is considered that the amount of exposure is reduced, and the diffusion of acid generated by exposure to the non-exposed portion is suppressed, whereby high resolution can be obtained.

<Photosensitized ray-sensitive or radiation-sensitive resin composition>

First, the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") will be described.

The composition of the present invention is typically a resist composition. Further, the composition of the present invention is typically a chemically amplified resist composition.

The composition of the present invention is used in a pattern forming method to be described later, and is any one of the following (i) or (ii) sensitizing ray-sensitive or radiation-sensitive resin compositions.

(i) a sensitizing ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "composition (i)") containing a resin (A1) (hereinafter also referred to as "resin (A1)"), wherein the resin (A1) contains a repeating unit having a group which generates a polar group by decomposition by an action of an acid, and a repeating unit containing a partial structure having no monovalent iodine atom which is not removed by irradiation with actinic rays or radiation; (ii) sensitizing ray or sensation containing a resin (A2) (hereinafter also referred to as "resin (A2)") and a compound (AD) having a monovalent iodine atom (hereinafter also referred to as "compound (AD)") a radiation-linear resin composition (hereinafter also referred to as "composition (ii)"), The resin (A2) contains a repeating unit having a group which generates a polar group by decomposition by an action of an acid.

<composition (i) and composition (ii), and resin (A1) and resin (A2)>

The resin (A1) contained in the composition (i) and the resin (A2) contained in the composition (ii) together contain a repeating unit having a group which generates a polar group by decomposition by an action of an acid.

Therefore, the resin (A) containing a repeating unit having a group which generates a polar group by decomposition by an action of an acid will be described below first.

The resin (A) described below corresponds to the resin (A2), and the resin (A) has a repeating unit having a partial structure having a monovalent iodine atom which is not removed by irradiation with actinic rays or radiation, which will be described later (hereinafter) The resin also referred to as "repeating unit (s)")" corresponds to the resin (A1).

<Resin (A)>

The resin (A) has an acid-decomposable repeating unit. The acid-decomposable repeating unit is, for example, a group which is decomposed by the action of an acid in the main chain or the side chain of the resin, or both the main chain and the side chain (hereinafter also referred to as "acid-decomposable group"). Repeat unit.

The composition of the present invention can be used as a positive resist composition or as a negative resist composition.

When the composition of the present invention is used as a negative resist composition, when the group generated by decomposition is a polar group, the developer containing the organic solvent is used. It is preferred because it has a low affinity and is insolubilized or insoluble (negative). Further, the polar group is more preferably an acidic group. The definition of the polar group is the same as the definition described in the section of the repeating unit (c) to be described later, and examples of the polar group which is decomposed by the acid-decomposable group include an alcoholic hydroxyl group, an amine group, an acidic group and the like.

The polar group which is decomposed by the acid-decomposable group is preferably an acidic group.

The acidic group is not particularly limited as long as it is insoluble in the developer containing the organic solvent, and is preferably a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, a fluorinated alcohol group, a sulfonylamino group or a sulfonium group. Amidino group, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)indolylene, bis(alkylcarbonyl)methylene, double (alkylcarbonyl) fluorenylene, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl) fluorenylene, tris(alkylcarbonyl)methylene, tris(alkyl sulfonate) More preferably, the mercapto group is a carboxylic acid group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a phenolic hydroxyl group, a sulfonic acid group or the like (previously used as a resist) The developing solution of the agent was 2.38 mass% of a dissociated group in an aqueous solution of tetramethylammonium hydroxide).

Preferred groups as the acid-decomposable group are groups in which a hydrogen atom of the group is substituted with a group which is desorbed by an acid.

Examples of the group which is detached by an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R). ₀₂ ) (OR ₃₉ ) and so on.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkyl group and an aryl group are combined. R ₃₆ and R ₃₇ may also be bonded to each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkyl group and an aryl group are combined.

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.

(a) a repeating unit having an acid-decomposable group

The resin (A) is preferably, for example, a repeating unit (a) having an acid-decomposable group in the main chain or the side chain of the resin or both the main chain and the side chain. The repeating unit (a) is more preferably a repeating unit represented by the following formula (V).

In the formula (V), R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. When R ₅₂ and L ₅ may be bonded to form a ring, R ₅₂ and L in the case of bonded _5, R ₅₂ represents an alkylene group.

L ₅ represents a single bond or a divalent linking group, and when it forms a ring with R ₅₂ , it represents a trivalent linking group.

R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. R ₅₅ and R ₅₆ may also be bonded to each other to form a ring. Wherein R ₅₅ and R _{56 are} not hydrogen atoms at the same time.

The general formula (V) will be described in more detail.

The alkyl group of R ₅₁ to R ₅₃ in the formula (V) is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a hexyl group, or a group which may have a substituent. An alkyl group having a carbon number of 20 or less, such as an ethylhexyl group, an octyl group or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, and particularly preferably an alkyl group having 3 or less carbon atoms.

The alkyl group contained in the alkoxycarbonyl group is preferably the same alkyl group as the alkyl group of R ₅₁ to R ₅₃ .

The cycloalkyl group may be a monocyclic type or a polycyclic type. Preferably, a cycloalkyl group having a substituent such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group having 3 to 10 carbon atoms and a monocyclic ring group may be mentioned.

The halogen atom may, for example, be a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a fluorine atom.

Preferred substituents of the respective groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, and an alkoxy group. The substituent, the thiol group, the fluorenyl group, the decyloxy group, the alkoxycarbonyl group, the cyano group, the nitro group and the like have a carbon number of preferably 8 or less.

Further, in the case where R ₅₂ is an alkyl group and forms a ring with L ₅ , the alkylene group is preferably a methylene group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group or the like. An alkyl group having 1 to 8 carbon atoms. More preferably, it is an alkylene group having 1 to 4 carbon atoms, and particularly preferably an alkylene group having 1 to 2 carbon atoms. The ring formed by the bonding of R ₅₂ and L _{5 is} preferably a 5-membered ring or a 6-membered ring.

R ₅₁ and R ₅₃ in the formula (V) are more preferably a hydrogen atom, an alkyl group or a halogen atom, and particularly preferably a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ) or a hydroxymethyl group (- CH ₂ -OH), chloromethyl (-CH ₂ -Cl), fluorine atom (-F). R _{52 is more} preferably a hydrogen atom, an alkyl group, a halogen atom or an alkyl group (forming a ring with L ₅ ), particularly preferably a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ) or a hydroxymethyl group. (-CH ₂ -OH), chloromethyl (-CH ₂ -Cl), a fluorine atom (-F), a methylene group (forming a ring with L ₅ ), and an ethyl group (forming a ring with L ₅ ).

Examples of the divalent linking group represented by L ₅ include an alkylene group, a divalent aromatic ring group, -COO-L ₁ -, -OL ₁ -, a group formed by combining two or more of these groups, and the like. . Here, L ₁ represents an alkyl group, a cycloalkyl group, a divalent aromatic ring group, and a group in which an alkyl group and a divalent aromatic ring group are combined.

L _{5 is} preferably a single bond, a group represented by -COO-L ₁ - or a divalent aromatic ring group. L _{1 is} preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group or a stretching propyl group. The divalent aromatic ring group is preferably a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 1,4-naphthyl group, and more preferably a 1,4-phenylene group. .

When the L ₅ and R _{52 are} bonded to each other to form a ring, the trivalent linking group represented by L ₅ is preferably exemplified by removing one arbitrary one from the specific example of the divalent linking group represented by L ₅ . a group of hydrogen atoms.

The alkyl group of R ₅₄ to R ₅₆ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group. An alkyl group having 1 to 4 carbon atoms such as butyl, isobutyl or t-butyl.

The cycloalkyl group represented by R ₅₅ and R ₅₆ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group or adamantane. a polycyclic cycloalkyl group such as a tetracycline or a tetracyclododecyl group.

Further, the ring formed by bonding R ₅₅ and R _{56 to} each other is preferably a ring having 3 to 20 carbon atoms, and may be a monocyclic ring such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group or an adamantyl group. a polycyclic ring such as a tetracyclodecyl group or a tetracyclododecyl group. When R ₅₅ and R ₅₆ are bonded to each other to form a ring, R _{54 is} preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

The aryl group represented by R ₅₅ and R ₅₆ is preferably an aryl group having 6 to 20 carbon atoms, and may be a monocyclic ring or a polycyclic ring or may have a substituent. For example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, etc. are mentioned. In the case where any of R ₅₅ and R ₅₆ is a hydrogen atom, it is preferred that the other is an aryl group.

The aralkyl group represented by R ₅₅ and R ₅₆ may be a single ring or a polycyclic ring or may have a substituent. The number of carbon atoms is preferably from 7 to 21, and examples thereof include a benzyl group and a 1-naphthylmethyl group.

The method for synthesizing a monomer corresponding to the repeating unit represented by the general formula (V) can be applied to a synthesis method of a usual polymerizable group-containing ester, and is not particularly limited.

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

In a specific example, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Rxa and Rxb each independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 19 carbon atoms. Z represents a substituent. p represents 0 or a positive integer, preferably 0 to 2, more preferably 0 or 1. When there are a plurality of cases where Z exists, they may be the same or different from each other. From the viewpoint of increasing the dissolution contrast in a developing solution containing an organic solvent (hereinafter also referred to as "organic developing solution") before and after acid decomposition, Z preferably includes only hydrogen atoms and carbon atoms. The group is, for example, preferably a linear or branched alkyl group or a cycloalkyl group.

Further, the resin (A) may further contain a repeating unit represented by the following formula (VI) as a repeating unit (a).

In the formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R ₆₂ may also bond with Ar ₆ to form a ring, and in this case, R ₆₂ represents a single bond or an alkylene group.

X ₆ represents a single bond, -COO- or -CONR ₆₄ -. R ₆₄ represents a hydrogen atom or an alkyl group.

L ₆ represents a single bond or an alkyl group.

Ar ₆ represents an (n+1)-valent aromatic ring group, and when it is bonded to R ₆₂ to form a ring, it represents an (n+2)-valent aromatic ring group.

In the case of n = 1, Y ₂ represents a group which is detached by the action of an acid. In the case of n ≧ 2, Y ₂ independently represents a hydrogen atom or a group which is detached by the action of an acid. Wherein at least one of Y ₂ represents a group which is detached by the action of an acid.

n represents an integer from 1 to 4.

The general formula (VI) will be described in more detail.

The alkyl group of R ₆₁ to R ₆₃ in the formula (VI) is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group or a hexyl group which may have a substituent. An alkyl group having a carbon number of 20 or less, such as an ethylhexyl group, an octyl group or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms.

The alkyl group contained in the alkoxycarbonyl group is preferably the same alkyl group as the alkyl group of R ₆₁ to R ₆₃ .

The cycloalkyl group may be a monocyclic type or a polycyclic type, and preferably a ring having a carbon number of 3 to 10 and a monocyclic ring such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group which may have a substituent. alkyl.

The halogen atom may, for example, be a fluorine atom, a chlorine atom or a bromine atom, and more preferably a fluorine atom.

In the case where R ₆₂ represents an alkylene group, the alkylene group preferably includes a methylene group which may have a substituent, an exoethyl group, a propyl group, a butyl group, a hexyl group, a octyl group and the like. ~8 alkyl groups.

The alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₆ may be the same alkyl group as the alkyl group of R ₆₁ to R ₆₃ .

X _{6 is} preferably a single bond, -COO-, -CONH-, more preferably a single bond, -COO-.

The alkylene group of L ₆ is preferably a methylene group which may have a substituent, an exoethyl group, a propyl group, a butyl group, a hexyl group, a octyl group, and the like, and an alkyl group having 1 to 8 carbon atoms. .

Ar ₆ represents an (n+1)-valent aromatic ring group. When the n is 1, the divalent aromatic ring group may have a substituent. For example, the following groups are preferred: a carbon number of 6 to 18 such as a phenyl group, a tolylene group, or a naphthyl group. Aryl group, or a divalent aromatic group containing a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, etc. Ring base. The ring formed by bonding R ₆₂ and Ar _{6 is} preferably a 5-membered ring or a 6-membered ring.

A specific example of the (n+1)-valent aromatic ring group in the case where n is an integer of 2 or more is preferably exemplified by (n-1) arbitrary from the specific example of the divalent aromatic ring group. a group of hydrogen atoms.

The (n+1)-valent aromatic ring group may also have a more substituent.

The alkyl group, the cycloalkyl group, the alkoxycarbonyl group, the alkylene group and the (n+1)-valent aromatic ring group described above may have a substituent which may be exemplified by the above formula (V) Specific examples in which the respective groups represented by R ₅₁ to R ₅₃ may have the same substituents.

n is preferably 1 or 2, more preferably 1.

Each of n Y ₂ independently represents a hydrogen atom or a group which is detached by the action of an acid. Among them, at least one of n represents a group which is detached by the action of an acid.

The group Y ₂ which is detached by the action of an acid may, for example, be -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(=O)-OC(R ₃₆ )(R ₃₇ )(R _{38 )} ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )-C(=O)-OC(R ₃₆ )(R ₃₇ )(R ₃₈ ), -CH (R ₃₆ ) (Ar) and the like.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkyl group and an aryl group are combined. R ₃₆ and R ₃₇ may also be bonded to each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkyl group and an aryl group are combined.

Ar represents an aryl group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be linear or branched, preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. N-butyl, t-butyl, hexyl, octyl and the like.

The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be a monocyclic type or a polycyclic type. The monocyclic type is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include an adamantyl group, a norbornyl group, an isoboronyl group, a camphanyl group, a dicyclopentyl group, and an α-pinene group. Base, tricyclodecylalkyl, tetracyclododecyl, androstanyl, and the like. Further, a part of the carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl group of R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ and Ar is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include an aryl group such as a phenyl group, a naphthyl group or a fluorenyl group, and a thiophene, a furan or a pyrrole group. a divalent aromatic ring group of a heterocyclic ring such as benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole or thiazole.

The group in which the alkyl group and the aryl group are combined with R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthalene group. Methyl group and the like.

The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The ring formed by bonding R ₃₆ and R _{37 to} each other may be a single ring type or a polycyclic type. The monocyclic type is preferably a cycloalkyl structure having a carbon number of 3 to 10, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, a cyclooctane structure, and the like. . The polycyclic type is preferably a cycloalkyl structure having 6 to 20 carbon atoms, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. Further, a part of the carbon atoms in the cycloalkyl structure may be substituted with a hetero atom such as an oxygen atom.

The respective groups of R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ and Ar may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, and a urea group. a base, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, etc., preferably having a carbon number It is 8 or less.

The group Y ₂ which is detached by the action of an acid is more preferably a structure represented by the following formula (VI-A).

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a group in which an alkyl group and an aryl group are combined.

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amine group, an ammonium group, a fluorenyl group, a cyano group or an aldehyde group.

At least two of Q, M, and L ₁ may also be bonded to form a ring (preferably a 5-member ring or a 6-member ring).

The alkyl group as L ₁ and L _{2 is} , for example, an alkyl group having 1 to 8 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, a hexyl group, or the like. Xinji.

The cycloalkyl group as L ₁ and L _{2 is} , for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

The aryl group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group, and an anthranyl group.

The group in which the alkyl group and the aryl group are combined with L ₁ and L ₂ is, for example, a carbon number of 6 to 20, and examples thereof include an aralkyl group such as a benzyl group or a phenethyl group.

The divalent linking group as M is, for example, an alkylene group (e.g., a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, etc.), a cycloalkyl group (e.g., a cyclopentyl group, Extending a cyclohexyl group, an adamantyl group, etc., an alkenyl group (for example, a vinyl group, a propenyl group, a butenyl group, etc.), a divalent aromatic ring group (for example, a phenyl group, a methylphenyl group, a naphthyl group) And), -S-, -O-, -CO-, -SO ₂ -, -N(R ₀ )-, and a divalent linking group obtained by combining a plurality of these groups. R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, a hexyl group, an octyl group, and the like).

The alkyl group as Q is the same as each of the groups as L ₁ and L ₂ .

Examples of the aliphatic hydrocarbon ring group containing no hetero atom and the aryl group containing no hetero atom in the cycloalkyl group which may contain a hetero atom of Q and the aryl group which may contain a hetero atom may be mentioned as L ₁ and L ₂ . The cycloalkyl group, the aryl group and the like are preferably a carbon number of 3 to 15.

Examples of the hetero atom-containing cycloalkyl group and the hetero atom-containing aryl group include a thiopyran, a cyclothiolane, a thiophene, a furan, a pyrrole, a benzothiophene, a benzofuran, a benzopyrrole, and the like. a group of a heterocyclic structure such as a triazine, an imidazole, a benzimidazole, a triazole, a thiadiazole, a thiazole or a pyrrolidone, if it is a structure generally called a hetero ring (a ring formed of carbon and a hetero atom, or The ring formed by a hetero atom is not limited to these groups.

Examples of the ring formed by bonding at least two of Q, M, and L ₁ include at least two bonds of Q, M, and L ₁ to form, for example, a propyl group and a butyl group to form a 5-membered ring containing an oxygen atom. Or the case of a 6-member ring.

Each group represented by L ₁ , L ₂ , M, and Q in the formula (VI-A) may have a substituent, and examples thereof include R ₃₆ to R ₃₉ , R ₀₁ , and R ₀₂ as described above. The substituent described for the substituent which may have Ar, the carbon number of the substituent is preferably 8 or less.

The group represented by -M-Q is preferably a group consisting of 1 to 30 carbon atoms, more preferably a group consisting of 5 to 20 carbon atoms.

The repeating unit represented by the above formula (VI) is preferably a repeating unit represented by the following formula (3).

In the formula (3), Ar ₃ represents an aromatic ring group.

R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a fluorenyl group or a heterocyclic group.

M ₃ represents a single bond or a divalent linking group.

Q ₃ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

At least two of Q ₃ , M ₃ and R ₃ may also be bonded to form a ring.

The aromatic ring group represented by Ar ₃ is the same as Ar ₆ in the above formula (VI) when n in the formula (VI) is ₁ , and more preferably a phenyl group or a naphthyl group. Further, it is better to stretch the phenyl group.

Ar ₃ may have a substituent, and the substituent which may be contained may be the same as the substituent which the Ar ₆ in the above-mentioned general formula (VI) may have.

The alkyl group or the cycloalkyl group represented by R ₃ has the same meaning as the alkyl group or cycloalkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ described above.

The aryl group represented by R ₃ has the same meaning as the aryl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ described above, and the preferred range is also the same.

The aralkyl group represented by R ₃ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The alkyl moiety of the alkoxy group represented by R _{3 is the same} as the alkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ described above, and the preferred range is also the same.

Examples of the fluorenyl group represented by R ₃ include a carbon number such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a amyl group, a trimethylethyl group, a benzamidine group, and a naphthyl group. The aliphatic thiol group of 1 to 10 is preferably an ethyl fluorenyl group or a benzamidine group.

The heterocyclic group represented by R ₃ may, for example, be a hetero atom-containing cycloalkyl group or a hetero atom-containing aryl group as described above, and is preferably a pyridine ring group or a pyran ring group.

R _{3 is} preferably an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a fluorenyl group or a heterocyclic group, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms (specific In terms of methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, tert-butyl, neopentyl, hexyl, 2-ethylhexyl, octyl), carbon number 3 ~15 cycloalkyl groups (specifically, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc.). R _{3 is} further preferably methyl, ethyl, isopropyl, t-butyl, t-butyl, neopentyl, cyclohexyl, adamantyl, cyclohexylmethyl or adamantylmethyl, especially preferably A Base, second butyl, neopentyl, cyclohexylmethyl or adamantylmethyl.

The alkyl group, cycloalkyl group, aryl group, arylalkyl group, alkoxy group, fluorenyl group or heterocyclic group described above may further have a substituent, and the substituent which may be present may be exemplified as described above. The substituents described by the substituents which R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ and Ar may have.

The divalent linking group represented by M ₃ has the same meaning as M in the structure represented by the above formula (VI-A), and the preferred range is also the same. M ₃ may have a substituent, and the substituent which M ₃ may have may be the same as the substituent which M in the structure represented by the above formula (VI-A) may have.

The alkyl group, the cycloalkyl group and the aryl group represented by Q ₃ have the same meanings as the alkyl group, the cycloalkyl group and the aryl group of Q in the structure represented by the above formula (VI-A), and The range is also the same.

The heterocyclic group represented by Q ₃ may, for example, be a hetero atom-containing cycloalkyl group of Q and a hetero atom-containing aryl group in the structure represented by the above formula (VI-A), and further preferably The scope is also the same.

Q ₃ may have a substituent, and the substituent which Q ₃ may have may be the same as the substituent which Q may have in the structure represented by the above formula (VI-A).

a ring formed by bonding at least two of Q ₃ , M ₃ and R ₃ to a ring formed by bonding at least two of Q, M, and L ₁ in the above formula (VI-A) For the same meaning, the preferred range is also the same.

Hereinafter, a specific example of the repeating unit represented by the general formula (VI) is shown as a preferred specific example of the repeating unit (a), but the present invention is not limited thereto.

The resin (A) is also preferably a repeating unit represented by the following formula (4).

In the formula (4), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L ₄ and R ₄₂ may be bonded to form a ring and, at the junction of the case ₄₂ and the L key R _4, R ₄₂ represents an alkylene group.

L ₄ represents a single bond or a divalent linking group, and represents a trivalent linking group in the case of forming a ring with R ₄₂ .

R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a fluorenyl group or a heterocyclic group.

M ₄ represents a single bond or a divalent linking group.

Q ₄ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

At least two of Q ₄ , M ₄ and R ₄₄ may also be bonded to form a ring.

R ₄₁ , R ₄₂ and R _{43 have the} same meanings as R ₅₁ , R ₅₂ and R ₅₃ in the above formula (V), and the preferred ranges are also the same.

L ₄ has the same meaning as L ₅ in the above formula (V), and the other preferred range is also the same.

R ₄₄ and R ₄₅ have the same meanings as R ₃ in the above formula (3), and the preferred ranges are also the same.

M ₄ has the same meaning as M ₃ in the above formula (3), and the preferred range is also the same.

Q ₄ has the same meaning as Q ₃ in the above formula (3), and the preferred range is also the same. The ring formed by bonding at least two of Q ₄ and M ₄ and R ₄₄ may be a ring formed by bonding at least two of Q ₃ , M ₃ and R ₃ , and the preferred range is also the same.

Specific examples of the repeating unit represented by the formula (4) are shown below, but the present invention is not limited thereto.

Further, the resin (A) may further contain a repeating unit represented by the following formula (BZ) as the repeating unit (a).

In the formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and AR may also be bonded to each other to form a non-aromatic ring.

R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

The aryl group of the AR is preferably an aryl group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group or a fluorenyl group, and more preferably an aryl group having 6 to 15 carbon atoms.

In the case where AR is a naphthyl group, an anthracenyl group or a fluorenyl group, the bonding position of the carbon atom to which Rn is bonded to the AR is not particularly limited. For example, in the case where AR is a naphthyl group, the carbon atom may be bonded to the α-position of the naphthyl group or may be bonded to the β-position. Or in the case where AR is a sulfhydryl group, the carbon atom may be bonded to the 1 position of the sulfhydryl group, or may be bonded to the 2 position or may be bonded to the 9 position.

The aryl group as AR may have one or more substituents each. Specific examples of such a substituent include carbon such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl and dodecyl. The number is 1~20 straight a chain or branched alkyl group, an alkoxy group containing the alkyl moiety, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkoxy group containing a cycloalkyl moiety, a hydroxyl group, a halogen atom, an aryl group, Cyano, nitro, decyl, decyloxy, decylamino, sulfonylamino, alkylthio, arylthio, aralkylthio, thiophenecarbonyloxy, thiophenemethylcarbonyloxy and pyrrole A heterocyclic residue such as a ketone residue. The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, an alkoxy group containing the alkyl group, and more preferably a p-methyl group or a p-methoxy group.

In the case where the aryl group as the AR has a plurality of substituents, at least two of the plurality of substituents may be bonded to each other to form a ring. The ring is preferably a 5-member ring to an 8-member ring, more preferably a 5-member ring or a 6-member ring. Further, the ring may be a hetero ring containing a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom in the ring member.

Further, the ring may have a substituent. The substituent may be the same as the group which will be described later as a further substituent which Rn may have.

Further, from the viewpoint of the roughness performance, the repeating unit (a) represented by the formula (BZ) preferably contains two or more aromatic rings. The number of the aromatic rings contained in the repeating unit is usually preferably 5 or less, more preferably 3 or less.

Further, in the repeating unit (a) represented by the formula (BZ), it is more preferable that the AR contains two or more aromatic rings from the viewpoint of the roughness performance, and it is more preferable that the AR is a naphthyl group or a biphenyl group. The number of the aromatic rings contained in the AR is usually preferably 5 or less, more preferably 3 or less.

As described above, Rn represents an alkyl group, a cycloalkyl group or an aryl group.

The alkyl group of Rn may be a linear alkyl group or a branched alkyl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a t-butyl group. An alkyl group having 1 to 20 carbon atoms such as a pentyl group, a hexyl group, a cyclohexyl group, an octyl group and a dodecyl group. The alkyl group of Rn is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

Examples of the cycloalkyl group of Rn include a cycloalkyl group having 3 to 15 carbon atoms such as a cyclopentyl group and a cyclohexyl group.

The aryl group of Rn is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a tolylmethyl group, a cumenyl group, a naphthyl group or a fluorenyl group.

Each of the alkyl group, the cycloalkyl group and the aryl group as Rn may further have a substituent. Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a decyl group, a decyloxy group, a decylamino group, a sulfonylamino group, a dialkylamino group, an alkylthio group, and an arylthio group. a heterocyclic residue such as an aralkylthio group, a thiophenecarbonyloxy group, a thiophenemethylcarbonyloxy group, and a pyrrolidone residue. Among them, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a decyl group, a decyloxy group, a decylamino group, and a sulfonylamino group are particularly preferable.

As described above, R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

Examples of the alkyl group and the cycloalkyl group of R ₁ include the same alkyl groups and cycloalkyl groups as described above for the alkyl group and the cycloalkyl group described for Rn. Each of the alkyl group and the cycloalkyl group may have a substituent. Examples of the substituent include the same substituents as described above for Rn.

In the case where R ₁ is an alkyl group or a cycloalkyl group having a substituent, preferred R _{1 is,} for example, a trifluoromethyl group, an alkoxycarbonylmethyl group, an alkylcarbonyloxymethyl group or a hydroxymethyl group. And alkoxymethyl.

The halogen atom of R ₁ may, for example, be a fluorine atom, a chlorine atom or a bromine atom. Among them, a fluorine atom is particularly preferred.

The alkyl moiety contained in the alkoxycarbonyl group of R ₁ can be, for example, the one exemplified above as the alkyl group of R ₁ .

It is preferred that Rn and AR are bonded to each other to form a non-aromatic ring, whereby the roughness performance can be further improved.

The non-aromatic ring formed by bonding Rn and AR to each other is preferably a 5-membered ring to an 8-membered ring, more preferably a 5-membered ring or a 6-membered ring.

The non-aromatic ring may be an aliphatic ring or a hetero ring containing a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom as a ring member.

The non-aromatic ring may also have a substituent. The substituent may, for example, be the same as the group described above with respect to the further substituent which Rn may have.

Specific examples of the repeating unit (a) represented by the general formula (BZ) are shown below, but are not limited to these specific examples.

Further, the aspect of the repeating unit having an acid-decomposable group different from the exemplified repeating unit may be a state in which a repeating unit of an alcoholic hydroxyl group is produced. In this case, it is preferably represented by at least one selected from the group consisting of the following general formulae (I-1) to (I-10). More preferably, the repeating unit is represented by at least one selected from the group consisting of the following general formulae (I-1) to (I-3), and further preferably represented by the following formula (I-1) ) said.

In the formula, Ra each independently represents a hydrogen atom, an alkyl group or a group represented by -CH ₂ -O-Ra ₂ . Here, Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group.

R ₁ represents a (n + 1) valent organic group.

In the case of m≧2, R ₂ independently represents a single bond or an (n+1)-valent organic group.

OP independently represents a group (acid-decomposable group) which generates an alcoholic hydroxyl group by decomposition of an acid. In the case of n≧2 and/or m≧2, two or more OPs may be bonded to each other to form a ring.

W represents a methylene group, an oxygen atom or a sulfur atom.

n and m represent an integer of 1 or more. Further, in the case where R ₂ represents a single bond in the formula (I-2), the formula (I-3) or the formula (I-8), n is 1.

l represents an integer greater than 0.

L ₁ represents a linking group represented by -COO-, -OCO-, -CONH-, -O-, -Ar-, -SO ₃ - or -SO ₂ NH-. Here, Ar represents a divalent aromatic ring group.

R independently represents a hydrogen atom or an alkyl group.

R ₀ represents a hydrogen atom or an organic group.

L ₃ represents a (m + 2) valent linking group.

In the case of m≧2, R ^L independently represents a (n+1)-valent linking group.

In the case of p≧2, R ^S independently represents a substituent. In the case of p≧2, a plurality of R ^S may be bonded to each other to form a ring.

p represents an integer from 0 to 3.

Ra represents a hydrogen atom, an alkyl group or a group represented by -CH ₂ -O-Ra ₂ . Ra is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group.

W represents a methylene group, an oxygen atom or a sulfur atom. W is preferably a methylene group or an oxygen atom.

R ₁ represents a (n + 1) valent organic group. R _{1 is} preferably a non-aromatic hydrocarbon group. In this case, R ₁ may be a chain hydrocarbon group or an aliphatic cyclic hydrocarbon group. R _{1 is more} preferably an aliphatic cyclic hydrocarbon group.

R ₂ represents a single bond or an (n+1)-valent organic group. R _{2 is} preferably a single bond or a non-aromatic hydrocarbon group. In this case, R ₂ may be a chain hydrocarbon group or an aliphatic cyclic hydrocarbon group.

In the case where R ₁ and/or R ₂ is a chain hydrocarbon group, the chain hydrocarbon group may be linear or branched. Further, the chain hydrocarbon group preferably has 1 to 8 carbon atoms. For example, in R ₁ and / or R ₂ is the case of alkylene, R ₁ and / or R ₂ is preferably a methylene group, an ethyl group stretching, stretch n-propyl, isopropyl extension, extending n-butyl, isobutyl stretch Butyl or a second butyl group.

In the case where R ₁ and/or R ₂ is an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be a monocyclic ring or a polycyclic ring. The aliphatic cyclic hydrocarbon group has, for example, a monocyclic, bicyclic, tricyclic or tetracyclic structure. The aliphatic cyclic hydrocarbon group has a carbon number of usually 5 or more, preferably 6 to 30, more preferably 7 to 25.

Examples of the aliphatic cyclic hydrocarbon group include a group having the partial structure listed below. Each of the partial structures may also have a substituent. Further, in each of the partial structures, the methylene group (-CH ₂ -) may also pass through an oxygen atom (-O-), a sulfur atom (-S-), a carbonyl group [-C(=O)-], or a sulfonium group. The group [-S(=O) ₂ -], the sulfinyl group [-S(=O)-] or the imido group [-N(R)-] (R is a hydrogen atom or an alkyl group) is substituted.

For example, when R ₁ and/or R ₂ is a cycloalkyl group, R ₁ and/or R _{2 are} preferably an adamantyl group, an extended adamantyl group, a decahydronaphthyl group, or a tricyclodecane. More preferably, a tetracyclododecyl group, an extended borneol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group or a cyclododecyl group, more preferably An adamantyl group, an extended borneol group, a cyclohexylene group, a cyclopentyl group, a tetracyclododecyl group or a tricyclodecyl group.

The non-aromatic hydrocarbon group of R ₁ and/or R ₂ may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, and an alkoxycarbonyl group having 2 to 6 carbon atoms. The alkyl group, alkoxy group and alkoxycarbonyl group may also have a more substituent. Examples of the substituent include a hydroxyl group, a halogen atom, and an alkoxy group.

L ₁ represents a linking group represented by -COO-, -OCO-, -CONH-, -O-, -Ar-, -SO ₃ - or -SO ₂ NH-. Here, Ar represents a divalent aromatic ring group. L _{1 is} preferably a linking group represented by -COO-, -CONH- or -Ar-, more preferably a linking group represented by -COO- or -CONH-.

R represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. R is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

R ₀ represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an alkynyl group, and an alkenyl group. R _{0 is} preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.

L ₃ represents a (m + 2) valent linking group. That is, L ₃ represents a trivalent or higher linking group. Examples of such a linking group include the corresponding groups in the specific examples described below.

R ^L represents a (n+1)-valent linking group. I.e., R ^L represents a divalent linking group above. Examples of such a linking group include an alkylene group, a cycloalkylene group, and a corresponding group in a specific example described below. R ^L may also be bonded to each other or to the following R ^S to form a ring structure.

R ^S represents a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, a decyloxy group, an alkoxycarbonyl group, and a halogen atom.

n is an integer of 1 or more. n is preferably an integer of 1 to 3, more preferably 1 or 2. Further, when n is set to 2 or more, the dissolution contrast in the developer containing the organic solvent can be further improved. Therefore, if it is set as such, the ultimate resolution and roughness characteristics can be further improved.

m is an integer of 1 or more. m is preferably an integer of 1 to 3, more preferably 1 or 2.

l is an integer greater than 0. l is preferably 0 or 1.

p is an integer from 0 to 3.

Specific examples of the repeating unit having a group which generates an alcoholic hydroxyl group by decomposition by an action of an acid are shown below. Further, in the specific examples, Ra and OP have the same meanings as in the general formulae (I-1) to (I-3), respectively. Further, when a plurality of OPs are bonded to each other to form a loop, the corresponding loop structure is expressed as "O-P-O" for the sake of convenience.

The group which is decomposed by the action of an acid to produce an alcoholic hydroxyl group is preferably represented by at least one selected from the group consisting of the following general formulae (II-1) to (II-4).

In the formula, R ₃ each independently represents a hydrogen atom or a monovalent organic group. R ₃ may also be bonded to each other to form a ring.

R ₄ each independently represents a monovalent organic group. R ₄ may also be bonded to each other to form a ring. R ₃ and R ₄ may also be bonded to each other to form a ring.

R ₅ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkynyl group. At least two R ₅ may also be bonded to each other to form a ring. In the case where one or two of the three R ₅ are a hydrogen atom, at least one of the remaining R ₅ represents an aryl group, an alkenyl group or an alkynyl group.

The group which is decomposed by the action of an acid to produce an alcoholic hydroxyl group is also preferably represented by at least one selected from the group consisting of the following general formulae (II-5) to (II-9). .

In the formula, R ₄ has the same meaning as R ₄ of the formula (II-1) to the formula (II-3).

R ₆ each independently represents a hydrogen atom or a monovalent organic group. R ₆ may also be bonded to each other to form a ring.

The group which is decomposed by the action of an acid to produce an alcoholic hydroxyl group is more preferably represented by at least one selected from the group consisting of the formula (II-1) to the formula (II-3), and further preferably by a formula ( It is represented by the formula (II-1) or the formula (II-3), and it is particularly preferably represented by the formula (II-1).

As described above, R ₃ represents a hydrogen atom or a monovalent organic group. R _{3 is} preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group.

The alkyl group of R ₃ may be linear or branched. The alkyl group of R ₃ preferably has 1 to 10 carbon atoms, more preferably 1 to ₃ carbon atoms. Examples of the alkyl group of R ₃ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group.

The cycloalkyl group of R ₃ may be a monocyclic ring or a polycyclic ring. The carbon number of the cycloalkyl group of R ₃ is preferably from 3 to 10, more preferably from 4 to 8. Examples of the cycloalkyl group of R ₃ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

Further, in the formula (II-1), at least one of R ₃ is preferably a monovalent organic group. By adopting such a configuration, a particularly high sensitivity can be achieved.

R ₄ represents a monovalent organic group. R _{4 is} preferably an alkyl group or a cycloalkyl group, more preferably an alkyl group. The alkyl group and the cycloalkyl group may also have a substituent.

The alkyl group of R ₄ preferably has no substituent or has one or more aryl groups and/or one or more decyl groups as a substituent. The unsubstituted alkyl group preferably has 1 to 20 carbon atoms. The alkyl group in the alkyl group substituted with one or more aryl groups preferably has 1 to 25 carbon atoms. The alkyl group in the alkyl group substituted by one or more decyl groups preferably has 1 to 30 carbon atoms. Further, when the cycloalkyl group of R ₄ does not have a substituent, the carbon number thereof is preferably from 3 to 20.

R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkynyl group. In the case where one or two of the three R ₅ are a hydrogen atom, at least one of the remaining R ₅ represents an aryl group, an alkenyl group or an alkynyl group. R _{5 is} preferably a hydrogen atom or an alkyl group. The alkyl group may have a substituent or may have no substituent. In the case where the alkyl group does not have a substituent, the carbon number thereof is preferably from 1 to 6, more preferably from 1 to 3.

As described above, R ₆ represents a hydrogen atom or a monovalent organic group. R _{6 is} preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or an alkyl group which may have a substituent. R _{6 is} preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and having no substituent.

Further, examples of the alkyl group and the cycloalkyl group of R ₄ , R ₅ and R ₆ include the same alkyl group and cycloalkyl group as the above-mentioned alkyl group and cycloalkyl group described for R ₃ .

Hereinafter, a specific example of a group which is decomposed by the action of an acid to produce an alcoholic hydroxyl group is shown.

Specific examples of the repeating unit having a group which generates an alcoholic hydroxyl group by decomposition by an action of an acid are shown below. In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

The repeating unit having an acid-decomposable group may be one type or two or more types may be used in combination.

The content of the repeating unit having an acid-decomposable group in the resin (A) (in the case of containing a plurality of cases) is preferably 5 mol% (% by mole) with respect to all the repeating units in the resin (A) The above is 80 mol% or less, more preferably 5 mol% or more and 75 mol% or less, further preferably 10 mol% or more and 65 mol% or less.

(b) a repeating unit represented by the formula (1)

The resin (A) preferably further contains a repeating sheet represented by the following formula (1) Yuan resin.

In the formula (1), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₃ may also be bonded to Ar ₁ to form a ring, and R _{13 in} this case represents an alkylene group.

X ₁ represents a single bond or a divalent linking group.

Ar ₁ represents an (n+1)-valent aromatic ring group, and when it is bonded to R ₁₃ to form a ring, it represents an (n+2)-valent aromatic ring group.

n represents an integer from 1 to 4.

Specific examples of the substituents which R ₁₁ , R ₁₂ and R ₁₃ in the formula (1), a cycloalkyl group, a halogen atom, an alkoxycarbonyl group and the groups may have and the formula (V) The specific examples described for each group represented by R ₅₁ , R ₅₂ and R _{53 in} the same are the same.

Ar ₁ represents an (n+1)-valent aromatic ring group. When the n is 1, the divalent aromatic ring group may have a substituent, and examples thereof include the following groups: a phenyl group, a methylphenyl group, a naphthyl group, a fluorene group, and the like. An aryl group of 18, or an aromatic ring containing a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole base.

A specific example of the (n+1)-valent aromatic ring group in the case where n is an integer of 2 or more is preferably exemplified by (n-1) arbitrary from the specific example of the divalent aromatic ring group. a group of hydrogen atoms.

The (n+1)-valent aromatic ring group may also have a more substituent.

The substituents which the above-mentioned alkylene group and the (n+1)-valent aromatic ring group may have include an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, and a hydroxypropoxy group. An alkoxy group such as a butyl group or a phenyl group.

The divalent linking group of X ₁ may be -COO- or -CONR ₆₄ -.

The alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₁ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group or a group which may have a substituent. An alkyl group having a carbon number of 20 or less, such as a butyl group, a second butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms.

X _{1 is} preferably a single bond, -COO-, -CONH-, more preferably a single bond, -COO-.

Ar _{1 is more} preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a benzene ring group, a naphthalene ring group, or a biphenyl group.

The repeating unit (b) preferably has a hydroxystyrene structure. That is, Ar _{1 is} preferably a benzene ring group.

n represents an integer of 1 to 4, preferably 1 or 2, more preferably 1 or more.

Specific examples of the repeating unit represented by the formula (1) are shown below, but the present invention is not limited thereto. Where a represents 1 or 2.

The resin (A) may contain two or more kinds of repeating units represented by the formula (1).

The content of the repeating unit represented by the formula (1) (total of the total amount) is preferably in the range of from 3 mol% to 98 mol%, more preferably 10 mol%, based on all the repeating units in the resin (A). In the range of 80 mol%, it is preferably in the range of 25 mol% to 70 mol%.

(c) a repeating unit having a polar group other than the repeating unit represented by the formula (1)

The resin (A) preferably contains a repeating unit (c) having a polar group. By containing the repeating unit (c), for example, the sensitivity of the resin-containing composition can be improved. The repeating unit (c) is preferably a non-acid-decomposable repeating unit (that is, having no acid-decomposable group).

Examples of the "polar group" which the repeating unit (c) can contain include the following (1) to (4). In the following description, the term "electricity" refers to the value of Pauling.

(1) A functional group having a structure in which an atom having an oxygen atom and an oxygen atom and a difference in electronegativity of 1.1 or more is bonded by a single bond

Examples of such a polar group include a group containing a structure represented by O-H such as a hydroxyl group. group.

(2) a functional group having a structure in which an atom having a difference between a nitrogen atom and a nitrogen atom and a nitrogen atom of 0.6 or more is bonded by a single bond

Examples of such a polar group include a group containing a structure represented by N-H such as an amine group.

(3) a functional group having a structure in which two atoms having a difference in electronegativity of 0.5 or more are bonded by a double bond or a triple bond

Examples of such a polar group include a group having a structure represented by C≡N, C=O, N=O, S=O or C=N.

(4) Functional groups having an ionic moiety

Examples of such a polar group include a group having a moiety represented by N ⁺ or S ⁺ .

Specific examples of the partial structure which the "polar group" can contain are listed below.

The "polar group" which the repeating unit (c) may contain is, for example, preferably at least one selected from the group consisting of (I) a hydroxyl group, (II) a cyano group, a (III) lactone group or a sultone group (cyclic sulfonate), (IV) a carboxylic acid group or a sulfonic acid group, (V) a decylamino group, a sulfonylamino group or a group corresponding to a derivative of such a group, VI) an ammonium group or a fluorenyl group, and a group obtained by combining two or more of these groups.

The polar group is preferably selected from the group consisting of a hydroxyl group, a cyano group, a lactone group, a sultone group, a carboxylic acid group, a sulfonic acid group, a decylamino group, a sulfonylamino group, an ammonium group, a fluorenyl group, and the groups. Among the two or more combined groups, an alcoholic hydroxyl group, a cyano group, a lactone group, a sultone group or a group having a cyanolactone structure is particularly preferable.

If the resin further contains a repeating unit having an alcoholic hydroxyl group, it can be further Exposure Latitude (EL) of a resin-containing composition.

When the resin further contains a repeating unit having a cyano group, the sensitivity of the resin-containing composition can be further improved.

When the resin further contains a repeating unit having a lactone group or a sultone group, the dissolution contrast in the developer containing the organic solvent can be further improved. Further, by setting in this manner, the dry etching resistance, the coating property, and the adhesion to the substrate of the resin-containing composition can be further improved.

When the resin further contains a repeating unit having a group which further has a dissolution contrast in a developing solution containing an organic solvent, the group contains a lactone structure having a cyano group. Further, by setting in this manner, the sensitivity of the resin-containing composition, the dry etching resistance, the coatability, and the adhesion to the substrate can be further improved. Further, by setting in this way, a single repeating unit can assume the functions obtained by the respective cyano group and the lactone group, and the design freedom of the resin can be further increased.

In the case where the polar group of the repeating unit (c) is an alcoholic hydroxyl group, it is preferably at least one selected from the group consisting of the following general formula (I-1H) to the general formula (I-10H). One said. More preferably, it is represented by at least one selected from the group consisting of the following general formula (I-1H) to the general formula (I-3H), and further preferably by the following general formula (I-1H) Said.

Wherein, Ra, R ₁ , R ₂ , W, n, m, l, L ₁ , R, R ₀ , L ₃ , R ^L , R ^S and p and the formula (I-1) to formula (I -10) are the same meanings respectively.

a repeating unit having a group which generates an alcoholic hydroxyl group by decomposition by an action of an acid, and a group selected from the group consisting of the general formula (I-1H) to the general formula (I-10H) When at least one of the repeating units is used in combination, for example, the sensitivity of the alcoholic hydroxyl group to the diffusion of the acid and the group which generates the alcoholic hydroxyl group by the decomposition of the acid can be increased, and the sensitivity is not increased. Improved exposure latitude (EL) in the case of other performance degradation.

The content of the repeating unit having an alcoholic hydroxyl group is preferably from 1 mol% to 60 mol%, more preferably from 3 mol% to 50 mol%, even more preferably from 5 mol% to 40 mol%, based on all the repeating units in the resin (A).

Specific examples of the repeating unit represented by any one of the formula (I-1H) to the formula (I-10H) are shown below. Further, in a specific example, Ra has the same meaning as Ra of the formula (I-1H) to the formula (I-10H).

In the case where the polar group of the repeating unit (c) is an alcoholic hydroxyl group or a cyano group, a preferred embodiment of the repeating unit may be a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. In this case, it is preferred that the acid-decomposable group is not provided. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group is preferably an adamantyl group, a diadamantyl group or a norbornyl group. The preferred hydroxy or cyano substituted alicyclic hydrocarbon structure is preferably a partial structure represented by the following formula (VIIa) to formula (VIIc). Thereby, the substrate adhesion and the developer affinity are improved.

In the general formulae (VIIa) to (VIIc), R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. Among them, at least one of R ₂ c to R ₄ c represents a hydroxyl group. Preferably, one or two of R ₂ c to R ₄ c are hydroxyl groups, and the balance is a hydrogen atom. In the formula (VIIa), it is more preferred that two of R ₂ c to R ₄ c are a hydroxyl group, and the balance is a hydrogen atom.

The repeating unit having a partial structure represented by the general formulae (VIIa) to (VIIc) may be a repeating unit represented by the following general formula (AIIa) to formula (AIIc).

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

R ₂ c ~ R ₄ c in the general formula (VIIa) ~ formula (VIIc) in R ₂ c ~ R ₄ c have the same meaning.

The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group or may not contain the repeating unit, and in the case of containing the repeating unit, a repeating unit having a hydroxyl group or a cyano group with respect to all the repeating units in the resin (A) The content is preferably from 1 mol% to 60 mol%, more preferably from 3 mol% to 50 mol%, and still more preferably from 5 mol% to 40 mol%.

Specific examples of the repeating unit having a hydroxyl group or a cyano group are listed below, but the present invention is not limited to these specific examples.

The repeating unit (c) may also be a repeating unit having a lactone structure or a sultone structure as a polar group.

The repeating unit having a lactone structure or a sultone structure is more preferably a repeating unit represented by the following formula (AII).

In the formula (AII), Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent (preferably, carbon number 1 to 4).

Preferred substituents which the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. The halogen atom of Rb ₀ may, for example, be a fluorine atom, a chlorine atom or a bromine atom. Rb _{0 is} preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group or a divalent linking group obtained by combining these groups. Ab is preferably a single bond, a divalent linking group represented by -Ab ₁ -CO ₂ -.

Ab ₁ is a linear or branched alkyl, monocyclic or polycyclic cycloalkyl group, preferably a methylene group, an ethyl group, a cyclohexylene group, an adamantyl group, or a borneol group.

V represents a group having a lactone structure or a sultone structure.

The group having a lactone structure or a sultone structure may be used as long as it has a lactone structure or a sultone structure, and is preferably a lactone structure or a sultone structure of a 5-membered ring to a 7-membered ring. Preferably, the lactone structure or the sultone structure of the 5-membered ring to the 7-membered ring has a ring structure in the form of a bicyclic structure or a spiro ring structure. More preferably, it is represented by any one of the following formula (LC1-1) to formula (LC1-17). A repeating unit of a lactone structure represented by a lactone structure or any one of the following formula (SL1-1) or formula (SL1-2). Alternatively, the lactone structure or the sultone structure may be directly bonded to the main chain. Particularly preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), (LC1-14), (SL1- 1).

The lactone moiety or the sultone structure may have a substituent (Rb ₂ ) or may have no such substituent (Rb ₂ ). Preferred examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkylene having 2 to 8 carbon atoms. An oxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, or the like. More preferably, it is an alkyl group, a cyano group, or an acid-decomposable group having 1 to 4 carbon atoms. n ₂ represents an integer of 0 to 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 each other to form a ring.

Repeating units having a lactone structure or a sultone structure usually have optics As the isomer, any optical isomer can be used. Further, one optical isomer may be used alone, or a plurality of optical isomers may be used in combination. In the case where an optical isomer is mainly used, the optical purity (enantiomeric excess (ee)) is preferably 90% or more, more preferably 95% or more.

The resin (A) may contain a repeating unit having a lactone structure or a sultone structure or may not contain the repeating unit, and in the case of a repeating unit having a lactone structure or a sultone structure, the resin is relative to all the repeating units. The content of the repeating unit in (A) is preferably in the range of 1 mol% to 70 mol%, more preferably in the range of 3 mol% to 65 mol%, still more preferably in the range of 5 mol% to 60 mol%.

Specific examples of the repeating unit having a lactone structure or a sultone structure in the resin (A) are shown below, but the present invention is not limited thereto. In the formula, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

Further, the repeating unit (c) may have a polar group which is an acidic group and is also one of a particularly preferable aspect. Preferred acidic groups include phenolic hydroxyl groups, carboxylic acid groups, sulfonic acid groups, fluorinated alcohol groups (for example, hexafluoroisopropanol group), sulfonylamino groups, sulfonyl fluorenylene groups, and (alkanes). (Alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)indenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imine A bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl) fluorenylene group, a tris(alkylcarbonyl)methylene group, a tris(alkylsulfonyl)methylene group. Among them, the repeating unit (c) is more preferably a repeating unit having a carboxyl group. By containing a repeating unit having an acidic group, the resolution in the use of a contact hole is increased. The repeating unit having an acidic group is preferably any one of the following: a repeating unit derived from a repeating unit of acrylic acid or methacrylic acid directly bonded to a repeating unit on a resin main chain, or an acidic group bonded to a resin main via a linking group The repeating unit on the chain is further introduced into the end of the polymer chain by using a polymerization initiator or a chain transfer agent having an acidic group during polymerization. It is especially preferred to be a repeating unit derived from acrylic acid or methacrylic acid.

The acidic group which the repeating unit (c) may have may contain an aromatic ring or an aromatic ring, and in the case of containing an aromatic ring, it is preferably selected from an acidic group other than a phenolic hydroxyl group. In the case where the repeating unit (c) has an acidic group, the content of the repeating unit having an acidic group is preferably 30 mol% or less, more preferably 20 mol% or less, based on all the repeating units in the resin (A). When the resin (A) contains a repeating unit having an acidic group, the content of the repeating unit having an acidic group in the resin (A) is usually 1 mol% or more.

Specific examples of the repeating unit having an acidic group are shown below, but the present invention is not limited thereto.

In a specific example, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

(d) a repeating unit having a plurality of aromatic rings

The resin (A) may further contain a repeating unit (d) having a plurality of aromatic rings represented by the following formula (c1).

In the formula (c1), R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or a nitro group, Y represents a single bond or a divalent linking group, Z represents a single bond or a divalent linking group, and Ar represents an aromatic ring group. , p represents an integer of 1 or more.

The alkyl group as R ₃ may be linear or branched, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a t-butyl group. The n-pentyl group, the n-hexyl group, the n-heptyl group, the n-octyl group, the n-decyl group, the n-decyl group, and the isobutyl group may further have a substituent. Preferred substituents include an alkoxy group, a hydroxyl group, and a halogen atom. And a nitro group, etc., wherein the alkyl group having a substituent is preferably a CF ₃ group, an alkoxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, an alkoxymethyl group or the like.

The halogen atom of R ₃ may, for example, be a fluorine atom, a chlorine atom or a bromine atom, and more preferably a fluorine atom.

Y represents a single bond or a divalent linking group, and examples of the divalent linking group include an ether group (oxygen atom), a thioether group (sulfur atom), an alkylene group, an aryl group, a carbonyl group, a sulfide group, Sulfhydryl, -COO-, -CONH-, -SO ₂ NH-, -CF ₂ -, -CF ₂ CF ₂ -, -OCF ₂ O-, -CF ₂ OCF ₂ -, -SS-, -CH ₂ SO ₂ CH ₂ -, -CH ₂ COCH ₂ -, -COCF ₂ CO-, -COCO-, -OCOO-, -OSO ₂ O-, amine group (nitrogen atom), mercapto group, alkyl sulfonyl group, -CH =CH-, -C≡C-, an aminocarbonylamino group, an aminosulfonylamino group, or a group containing a combination of these groups. Y preferably has a carbon number of 15 or less, more preferably 10 or less carbon atoms.

Y is preferably a single bond, a -COO- group, a -COS- group, a -CONH- group, more preferably a -COO- group, a -CONH- group, and more preferably a -COO- group.

Z represents a single bond or a divalent linking group, and examples of the divalent linking group include an ether group (oxygen atom), a thioether group (sulfur atom), an alkylene group, an extended aryl group, a carbonyl group, a thioether group, a thiol group, -COO-, -CONH-, -SO ₂ NH-, amine group (nitrogen atom), mercapto group, alkyl sulfonyl group, -CH=CH-, aminocarbonylamino group, aminosulfonylamino group, Or a group comprising a combination of such groups.

Z is preferably a single bond, an ether group, a carbonyl group, -COO-, more preferably a single bond, an ether group, and particularly preferably a single bond.

Ar represents an aromatic ring group, and specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a quinolyl group, a furyl group, a thienyl group, an anthracenyl-9-one-yl group, an anthraquinonyl group, and a phenanthrenequinone group. A phenanthraquinonyl group, a pyrrolyl group or the like is preferably a phenyl group. The aromatic ring group may further have a substituent. Preferred substituents include, for example, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a decyl group, a decyloxy group, a decylamino group, and a sulfonium group. An aryl group such as an amino group, a phenyl group, an aryloxy group, an arylcarbonyl group, a heterocyclic residue or the like, in which the exposure latitude or pattern shape caused by out-band light is suppressed From the viewpoint of deterioration, a phenyl group is preferred.

p is an integer of 1 or more, preferably an integer of 1 to 3.

The repeating unit (d) is more preferably a repeating unit represented by the following formula (c2).

In the formula (c2), R ₃ represents a hydrogen atom or an alkyl group. The alkyl group which is an alkyl group represented by R ₃ is preferably the same as the alkyl group represented by R _{3 of} the formula (c1).

Here, regarding extreme ultraviolet (EUV light) exposure, there is a tendency to cause light leakage in the ultraviolet range of wavelengths of 100 nm to 400 nm (out-of-band The (out-of-band) light deteriorates the surface roughness, and as a result, the resolution and the line width roughness (LWR) performance are degraded by the bridge between the patterns or the disconnection of the pattern.

However, the aromatic ring in the repeating unit (d) functions as an internal filter that absorbs the out-of-band light. Therefore, from the viewpoint of high resolution and low LWR, the resin (A) preferably contains a repeating unit (d).

Here, from the viewpoint of obtaining high resolution, the repeating unit (d) preferably has no phenolic hydroxyl group (hydroxyl group directly bonded to the aromatic ring).

Specific examples of the repeating unit (d) are shown below, but are not limited to these specific examples.

The resin (A) may contain the repeating unit (d) or the repeating unit (d), and in the case of containing the repeating unit (d), the content of the repeating unit (d) with respect to all the repeating units of the resin (A) It is preferably in the range of 1 mol% to 30 mol%, more preferably in the range of 1 mol% to 20 mol%, still more preferably in the range of 1 mol% to 15 mol%. The repeating unit (d) contained in the resin (A) may be contained in combination of two or more kinds.

The resin (A) of the present invention may suitably contain the repeating unit (a)~ Repeating units other than unit (d) are repeated. The repeating unit having an alicyclic hydrocarbon structure containing no polar group (for example, the acid group, a hydroxyl group, or a cyano group) and having no acid decomposition property may be further included as an example of such a repeating unit. Thereby, the solubility of the resin can be appropriately adjusted at the time of development using a developing solution containing an organic solvent. Such a repeating unit can be exemplified by the repeating unit represented by the formula (IV).

In the 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 a fluorenyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

The cyclic structure of R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group, and a cycloalkenyl group having 3 to 12 carbon atoms such as a cyclohexenyl group. A preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group contains a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the cyclic hydrocarbon group include a dicyclohexyl group, a perhydronaphthyl group and the like. Examples of the crosslinked cyclic hydrocarbon ring include decane, borneane, norbornane, norbornane, and bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring, etc.). Equivalent bicyclic hydrocarbon ring, and tricyclo [5.2.1.0 ^3,8 ]nonane (homobrendane), adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[4.3.1.1 ^2,5 ] a tricyclic hydrocarbon ring such as undecane ring, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane, perhydro-1,4-bridged methylene-5,8-bridge methylene A tetracyclic hydrocarbon ring such as a perhydro-1,4-methano-5, 8-methanonaphthalene ring or the like. In addition, the cross-linked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroquinone, perhydrophenanthrene, perhydrohydroquinone, perhydrohydroquinone, perhydrohydroquinone, A condensed ring obtained by condensation of a total of 5 to 8 membered cycloalkane rings, such as a perhydroanthracene ring.

Preferred examples of the crosslinked cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctyl group, a tricyclo[5.2.1.0 ^2,6 ]decyl group, and the like. More preferably, the crosslinked cyclic hydrocarbon ring may be a norbornyl group or an adamantyl group.

The alicyclic hydrocarbon group may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, an amine group substituted with a hydrogen atom, and the like. A preferred halogen atom is a bromine atom, a chlorine atom or a fluorine atom. Preferred alkyl groups include a methyl group, an ethyl group, a butyl group and a tert-butyl group. The alkyl group may further have a substituent, and examples of the substituent which may be further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amine group substituted with a hydrogen atom.

Examples of the substituent of the hydroxyl group and the hydrogen atom in the amine group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkoxy group. Alkylcarbonyl. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, and preferred substituted methyl groups include methoxymethyl, methoxythiomethyl and benzyloxy groups. Methyl, tert-butoxymethyl, 2-methoxyethoxymethyl, preferred substituted ethyl can be exemplified by 1-ethoxyethyl, 1-methyl-1-methoxy The ethyl group, preferably a fluorenyl group, may be an aliphatic fluorenyl group having 1 to 6 carbon atoms such as a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a pentamidine group or a trimethyl acetyl group. The oxycarbonyl group may, for example, be an alkoxycarbonyl group having 1 to 4 carbon atoms.

The resin (A) may contain a repeating unit having a polar group-free alicyclic hydrocarbon structure, exhibiting no acid decomposition property, or may not contain the repeating unit, and in the case of containing the repeating unit, relative to the resin (A) The content of the repeating unit in all the repeating units is preferably from 1 mol% to 20 mol%, more preferably from 5 mol% to 15 mol%.

Specific examples of the repeating unit having an alicyclic hydrocarbon structure containing no polar group and exhibiting no acid decomposition property are listed below, but the present invention is not limited to these specific examples. In the formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

Further, the resin (A) may further contain a repeating unit represented by the following formula (5).

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. S represents a structural portion which is decomposed by irradiation of actinic rays or radiation to generate an acid in a side chain.

Specific examples of the repeating unit represented by the formula (5) are shown below, but the present invention is not limited thereto.

The content of the repeating unit represented by the formula (5) in the resin (A) is preferably in the range of 1 mol% to 40 mol%, more preferably in the range of 2 mol% to 30 mol%, based on all the repeating units of the resin (A). It is particularly preferably in the range of 5 mol% to 25 mol%.

Further, the resin (A) may contain the following monomer components in view of an effect of an increase in Tg or an improvement in dry etching resistance, an internal filter having external light as described above, and the like.

In the resin (A) used in the composition of the present invention, it is usually necessary to adjust the dry etching resistance of the resist or the standard developer suitability, substrate adhesion, resist profile, and further as a resist. The resolution, heat resistance, sensitivity, and the like of the performance are appropriately set, and the molar ratio of each repeating structural unit is appropriately set.

Specific examples of the resin (A) are shown below, but the present invention is not limited thereto.

The form of the resin (A) in the present invention may be any of a random type, a block type, a comb type, and a star type.

The resin (A) can be synthesized, for example, by radical polymerization, cationic polymerization or anionic polymerization of an unsaturated monomer corresponding to each structure. Further, after the polymerization is carried out using an unsaturated monomer corresponding to the precursor of each structure, a polymer reaction is carried out to obtain a target resin.

For example, a general synthesis method is an overall polymerization method in which an unsaturated monomer and a polymerization initiator are dissolved in a solvent and heated to carry out polymerization; and the unsaturated solvent is added dropwise in 1 hour to 10 hours in a heating solvent. The dropwise addition polymerization method of the solution of the monomer and the polymerization initiator is preferably a dropping polymerization method.

The solvent to be used in the polymerization is, for example, a solvent which can be used in the preparation of a sensitizing ray-sensitive or radiation-sensitive resin composition described later, and more preferably used and used. It is preferred to carry out the polymerization by using the same solvent as the solvent used in the composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, or the like) can be used to initiate polymerization. The radical initiator is preferably an azo initiator, and more preferably an azo initiator having an ester group, a cyano group or a carboxyl group. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), and the like. The polymerization may also be carried out in the presence of a chain transfer agent (for example, an alkyl mercaptan or the like) as needed.

The concentration of the reaction is from 5% by mass to 70% by mass, preferably from 10% by mass to 50% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 40 ° C to 100 ° C.

The reaction time is usually from 1 hour to 48 hours, preferably from 1 hour to 24 hours, more preferably from 1 hour to 12 hours.

After completion of the reaction, the mixture was allowed to cool to room temperature and purified. Purification can be carried out by a usual method such as the following method: liquid-liquid extraction method in which residual monomer or oligomer component is removed by washing with water or a suitable solvent; only a solution having a specific molecular weight or less is removed by ultrafiltration or the like. a purification method; or a reprecipitation method in which a resin is solidified in a poor solvent by dropping a resin solution into a poor solvent, thereby removing residual monomers or the like; or a resin slurry separated by filtration using a poor solvent A purification method or the like in a solid state such as washing is performed. For example, a solvent (poor solvent) in which the resin is poorly soluble or insoluble is preferably 10 times or less the volume of the reaction solution, preferably The reaction solution was contacted in a volume of 10 times to 5 times, and the resin was precipitated as a solid.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation in the polymer solution may be a poor solvent of the polymer, and may be derived from a hydrocarbon, a halogenated hydrocarbon, a nitro compound, depending on the kind of the polymer. An ether, a ketone, an ester, a carbonate, an alcohol, a carboxylic acid, water, a mixed solvent containing these solvents, and the like are appropriately selected and used. Among these solvents, the precipitating or reprecipitation solvent is preferably a solvent containing at least an alcohol (particularly methanol or the like) or water.

The amount of the precipitation or reprecipitation solvent to be used may be appropriately selected in consideration of efficiency, productivity, and the like, and is usually 100 parts by mass to 10,000 parts by mass, preferably 200 parts by mass to 2000 parts by mass, per 100 parts by mass of the polymer solution. More preferably, it is 300 mass parts to 1000 mass parts.

The temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency or workability, and is usually about 0 ° C to 50 ° C, preferably near room temperature (for example, about 20 ° C to 35 ° C). The precipitation or reprecipitation operation can be carried out by a known method such as a batch type or a continuous type using a conventional mixing container such as a stirring tank.

The precipitated or reprecipitated polymer is usually subjected to conventional solid-liquid separation such as filtration or centrifugation, and dried for use. Filtration is a solvent-resistant filter material, preferably under pressure. The drying is carried out at a temperature of from about 30 ° C to about 100 ° C, preferably from about 30 ° C to about 50 ° C under normal pressure or reduced pressure (preferably under reduced pressure).

Further, the resin may be precipitated and separated once, and then dissolved again in a solvent to be in contact with a solvent in which the resin is poorly soluble or insoluble. That is, it can also be included a method of the following steps: after the end of the radical polymerization reaction, the polymer is insoluble or insoluble solvent is contacted with the polymer to precipitate the resin (step a); the resin is separated from the solution (step b); The resin solution A is prepared by redissolving in a solvent (step c); thereafter, the solvent in which the resin is poorly soluble or insoluble is less than 10 times the volume of the resin solution A (preferably a volume of 5 times or less) The resin solution A is contacted to thereby precipitate a resin solid (step d); and the precipitated resin is separated (step e).

The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, or the like) can be used to initiate polymerization. The radical initiator is preferably an azo initiator, and more preferably an azo initiator having an ester group, a cyano group or a carboxyl group. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), and the like. The initiator is added in an additional or batchwise manner as needed, and after completion of the reaction, it is introduced into a solvent, and the desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is from 5% by mass to 50% by mass, preferably from 10% by mass 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 molecular weight of the resin (A) of the present invention is not particularly limited, but preferably has a weight average molecular weight of from 1,000 to 100,000, more preferably from 1,500 to 60,000, still more preferably from 2,000 to 30,000. By setting the weight average molecular weight to a range of from 1,000 to 100,000, deterioration of heat resistance or dry etching resistance can be prevented, and deterioration of developability or viscosity can be prevented, and film formability can be deteriorated. Here, the weight average molecular weight of the resin is represented by gel permeation chromatography (Gel Permeation) Chromatography, GPC) (carrier: Tetrahydrofuran (THF) or N-methyl-2-pyrrolidone (NMP)).

Further, the degree of dispersion (Mw/Mn) is preferably from 1.00 to 5.00, more preferably from 1.00 to 3.50, and still more preferably from 1.00 to 2.50. When the molecular weight distribution is small, the resolution and the resist shape are excellent, and the side walls of the resist pattern are smooth and excellent in roughness.

In the present specification, the weight average molecular weight (Mw) and the degree of dispersion of the resin can be obtained, for example, by using HLC-8120 (manufactured by Tosoh Corporation) and using TSKgel Multipore HXL-M (manufactured by Tosoh Corporation). 7.8 mm ID × 30.0 cm) was used as a column, and tetrahydrofuran (THF) or N-methyl-2-pyrrolidone (NMP) was used as a solution.

<Resin (A2)>

The resin (A) is described above, and as described above, the resin (A) corresponds to the resin (A2) contained in the composition (ii).

In the composition (ii), the resin (A2) as the resin (A) may be used alone or in combination of two or more. The content of the resin (A2) as the resin (A) is preferably 20% by mass to 99% by mass, and more preferably 30% by mass to 99% by mass based on the total solid content in the component (ii). Good is 40% by mass to 99% by mass.

<(s) repeating unit having a monovalent iodine atom>

Next, the repeating unit (s) will be described.

The resin (A1) contained in the composition (i) is a resin containing a repeating unit (s) having a monovalent iodine atom, and it is preferred to have the above-mentioned resin (A) having a repeating single Yuan (s) resin. In this case, the resin (A1) is the same as the above-mentioned resin (A) except for the repeating unit (s).

In more detail, the repeating unit (s) is a repeating unit having a partial structure having no monovalent iodine atom which is detached by irradiation with actinic rays or radiation. That is, the repeating unit (s) contains a partial structure having a monovalent iodine atom (hereinafter also referred to as "partial structure (s1)"), but the partial structure (s1) is not irradiated by actinic rays or radiation. The partial structure in which the unit (s) is detached. It is considered that the partial structure (s1) having a monovalent iodine atom does not escape even if it is irradiated with actinic rays or radiation, so that the effect of light absorption is not lowered and high sensitivity can be obtained.

Here, a partial structure in which decomposition by irradiation of actinic rays or radiation is explained will be described.

In the repeating unit (s) having a monovalent iodine atom, the partial structure (s1) having a monovalent iodine atom is preferably not contained in a partial structure which is decomposed by irradiation with actinic rays or radiation.

The partial structure which is decomposed by the irradiation of actinic rays or radiation can be, for example, a partial structure represented by the following general formulae (I) to (III). Further, by irradiation with actinic rays or radiation, the S atom-S atom bond in the general formula (I) is cleaved, and the O atom-N atom bond in the general formula (II) is cleaved, and the O atom in the general formula (III) is The N atom bond is broken.

In the general formulae (I) to (III), Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.

R ₂₀₆ , R ₂₀₇ and R ₂₀₈ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted extended alkenyl group or a substituted or unsubstituted extended aryl group.

Further, the repeating unit (s) having a monovalent iodine atom may also be a repeating unit having an acid-decomposable group. That is, in the repeating unit (s), the partial structure (s1) having a monovalent iodine atom is not excluded as a partial structure in which a polar group is generated by decomposition of an acid.

In this case, the resin (A1) may contain only the repeating unit (s), and may not contain the repeating unit (a) having an acid-decomposable group as described above. In other words, in the resin (A1) in this case, "a repeating unit having a partial structure having a monovalent iodine atom which is not removed by irradiation with actinic rays or radiation" also serves as "having a polarity due to decomposition by an action of an acid. a repeating unit of a group."

Such a repeating unit (s) is preferably, for example, a repeating unit represented by the following formula (1').

In the formula (1'), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₃ and Ar ₁ may be bonded to form a ring and, at the case of the resultant bond R ₁₃ and Ar _1, R ₁₃ represents an alkylene group.

X ₁ represents a single bond, an alkyl group, an aromatic ring group, -O-, -S-, -CO-, -COO-, -SO ₂ NH-, -SO ₂ O-, -NR- (R is a hydrogen atom) Or an alkyl group, a divalent nitrogen-containing non-aromatic heterocyclic group, or a divalent linking group comprising a combination of these groups.

Ar ₁ represents an aromatic ring group.

RI represents an iodine atom or an organic group containing at least one iodine atom.

n represents an integer of 1 or more.

In the formula (1'), the alkyl group represented by R ₁₁ to R ₁₃ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group or a second butyl group which may have a substituent. An alkyl group having a carbon number of 20 or less, such as a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, and particularly preferably an alkyl group having 3 or less carbon atoms.

The alkyl group contained in the alkoxycarbonyl group is preferably the same alkyl group as the alkyl group of R ₁₁ to R ₁₃ .

The cycloalkyl group may be a monocyclic type or a polycyclic type. Preferably, a ring having a carbon number of 3 to 10 and a monocyclic ring such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group which may have a substituent alkyl.

Examples of the halogen atom include halogen atoms other than the iodine atom.

In the case where R ₁₃ is bonded to Ar ₁ to form a ring, examples of the alkylene group include a methylene group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a octyl group. The alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms.

Examples of the alkylene group represented by X ₁ include a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, and the like, and an alkyl group having 1 to 8 carbon atoms, preferably a carbon number. The alkyl group of 1 to 4 is more preferably an alkyl group having 1 to 2 carbon atoms.

The aromatic ring group represented by X ₁ is a divalent aromatic ring group, and examples thereof include 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, and 1,4-naphthyl. And, preferably, it is a 1,4-phenylene group.

The alkyl group represented by R in -NR- represented by X ₁ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a hexyl group, or the like which may have a substituent. An alkyl group having a carbon number of 20 or less, such as an ethylhexyl group, an octyl group or a dodecyl group, is preferably an alkyl group having a carbon number of 8 or less.

The divalent nitrogen-containing non-aromatic heterocyclic group represented by X ₁ is preferably a group obtained by removing two arbitrary hydrogen atoms from a hetero ring such as pyrrole, pyrrolidine or piperidine.

In these groups, X _{1 is} preferably a single bond, -COO-, -NR-, a divalent linking group containing a combination of these groups, more preferably -COO-.

The aromatic ring group represented by Ar ₁ is an (n+1)-valent aromatic ring group.

Examples of the divalent aromatic ring group in the case where n is 1, for example, the following groups are preferred examples: a phenyl group having 6 to 18 carbon atoms such as a phenyl group, a methylphenyl group, an anthranyl group, and a fluorenyl group. Or an aromatic ring group containing a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole or thiazole.

A specific example of the (n+1)-valent aromatic ring group in the case where n is an integer of 2 or more is preferably exemplified by (n-1) arbitrary from the specific example of the divalent aromatic ring group. a group of hydrogen atoms.

The (n+1)-valent aromatic ring group may also have a more substituent.

Examples of the substituent which the (n+1)-valent aromatic ring group may have include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, and the like. A halogen atom (excluding an iodine atom), an alkoxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group or a nitro group, and the number of carbon atoms of the substituent is preferably 8 or less.

The aromatic ring group represented by Ar ₁ is preferably a group in which a phenyl group, a naphthyl group, and (n-1) arbitrary hydrogen atoms are removed from the groups.

Examples of the organic group containing at least one iodine atom represented by RI include an iodoalkyl group such as 2-iodoethyl or 3-iodopropyl.

RI is preferably an iodine atom.

n represents an integer of 1 or more. The upper limit of the integer represented by n is equal to the number of replaceable hydrogen atoms in the aromatic ring group represented by Ar ₁ .

In the case where the sensitivity is higher and the resolution is higher, n is preferably an integer of 2 or more, and more preferably an integer of 3 or more.

Specific examples of the repeating unit (s) having a monovalent iodine atom are shown below, but the present invention is not limited thereto.

In the resin (A1), the repeating unit (s) may be used alone or in combination of two or more.

The content of the repeating unit (s) in the resin (A1) (in the case of containing a plurality of cases) is preferably from 0.1 mol% to 80 mol%, more preferably, based on all the repeating units in the resin (A1). 0.1 mol% to 50 mol%, and further preferably 1 mol% ~30mol%.

<Resin (A1)>

The resin (A1) contained in the composition (i) may be used alone or in combination of two or more. The content of (A1) is preferably from 25% by mass to 99% by mass, more preferably from 30% by mass to 99% by mass, even more preferably from 40% by mass to 99%, based on the total solid content of the component (i). quality%.

<(AD) Compound having a monovalent iodine atom>

Next, the compound (AD) having a monovalent iodine atom contained in the composition (ii) will be described. The compound (AD) is preferably, for example, (AD1) a resin having a monovalent iodine atom (hereinafter also referred to as "resin (AD1)"), and (AD2) a low molecular compound having a monovalent iodine atom (hereinafter also It is called "low molecular compound (AD2)").

<(AD1) Resin having a monovalent iodine atom>

The resin (AD1) having a monovalent iodine atom contained in the composition (ii) is preferably exemplified by containing the repeating unit (s) having a monovalent iodine atom as described above, and does not contain the above. (a) a resin having a repeating unit of an acid-decomposable group.

The content of the repeating unit (s) in the resin (AD1) (in total of a plurality of cases) is preferably from 5 mol% to 100 mol%, more preferably 10 mol, based on all the repeating units in the resin (AD1). %~100mol%, and further preferably 20mol%~100mol%.

Further, the resin (AD1) may contain the same repeating unit as the repeating unit described in the repeating unit which may be contained in the resin (A), and the content of the repeating unit in the resin (AD1) is also the same as that of the resin (A).

In the composition (ii), the resin (AD1) may be used alone or in combination of two or more. The content of the resin (AD1) is preferably 0.1% by mass to 50% by mass based on the total solid content in the component (ii), more preferably 0.1% by mass to 30% by mass, and still more preferably 1% by mass. 10% by mass.

<(AD2) Low Molecular Compound with Monovalent Iodine Atom>

The low molecular compound (AD2) having a monovalent iodine atom may, for example, be a compound having a molecular weight of less than 3,000 having a monovalent iodine atom, preferably a compound having a molecular weight of less than 2,000, more preferably a compound having a molecular weight of less than 1,500, and further preferably having a molecular weight of less than 1,500. 1000 compounds. The low molecular compound (AD2) having a monovalent iodine atom is, for example, a compound represented by the following formula (2').

Ar ₂ -(RI) _n (2')

In the formula (2'), Ar ₂ represents an n-valent aromatic ring group.

RI represents an iodine atom or an organic group containing at least one iodine atom.

n represents an integer of 1 or more.

The aromatic ring group represented by Ar ₂ is an n-valent aromatic ring group.

The monovalent aromatic ring group in the case where n is 1, for example, the following groups are preferable: a carbon number such as a phenyl group, a tolyl group, a naphthyl group, an anthracenyl group, a biphenyl group or a stilbene group. 6 to 18 aryl groups, or contain, for example, thiophene, furan, pyrrole, benzothiophene, A heterocyclic aromatic ring group such as benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole or triphenylamine.

A specific example of the n-valent aromatic ring group in the case where n is an integer of 2 or more is preferably exemplified by removing (n-1) arbitrary hydrogen atoms from the specific example of the monovalent aromatic ring group. Group.

The n-valent aromatic ring group may also have a more substituent.

Examples of the substituent which the n-valent aromatic ring group may have include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, and a halogen atom (iodine). The atomic number, the alkoxy group, the thioether group, the decyl group, the decyloxy group, the alkoxycarbonyl group, the cyano group, the nitro group and the like are preferably 8 or less.

The organic group containing at least one iodine atom represented by RI may, for example, be an iodoalkyl group such as 2-iodoethyl or 3-iodopropyl.

RI is preferably an iodine atom.

n represents an integer of 1 or more. The upper limit of the integer represented by n is equal to the number of hydrogen atoms which can be substituted in the aromatic ring group represented by Ar ₂ .

n is preferably an integer of 2 or more, and more preferably an integer of 3 or more.

Specific examples of the low molecular compound (AD2) are shown below, but the present invention is not limited thereto.

In the composition (ii), the low molecular compound (AD2) may be used alone or in combination of two or more.

The content of the low molecular compound (AD2) in the composition (ii) is preferably from 0.1% by mass to 50% by mass, more preferably from 0.1% by mass to 30% by mass based on the total solid content of the component (ii). %, and further preferably 1% by mass to 10% by mass.

<common ingredients>

Next, the components which the composition (the composition (i) and the composition (ii)) of the present invention can be contained together will be described.

[1] (B) Compounds which generate acid by irradiation with actinic rays or radiation

The composition of the present invention preferably contains a compound which generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as "acid generator" and "acid-producing compound". (B)").

The acid generator is not particularly limited as long as it is a known acid generator, and it is preferred to generate an organic acid such as sulfonic acid or bis(alkylsulfonyl) ruthenium by irradiation with actinic rays or radiation. At least any one of tris(alkylsulfonyl)methide.

The compound (B) which generates an acid by irradiation with actinic rays or radiation may be in the form of a low molecular compound or may be in a form incorporated into a part of the polymer. Further, the form of the low molecular compound may be used in combination with the form incorporated in a part of the polymer.

In the case where the compound (B) which generates an acid by irradiation with actinic rays or radiation is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.

When the compound (B) which generates an acid by irradiation with actinic rays or radiation is in a form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (A) described above to constitute a part. The resin (A) may be incorporated into a resin different from the resin (A).

More preferably, it is a compound represented by the following general formula (ZI), general formula (ZII), and general formula (ZIII).

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a carbon number of usually 1 to 30, preferably 1 to 20.

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring. The group formed by bonding two of R ₂₀₁ to R ₂₀₃ may, for example, be an alkyl group (for example, a butyl group or a pentyl group).

Z ^- represents a non-nucleophilic anion (an anion having a significantly lower ability to cause a nucleophilic reaction).

Examples of the non-nucleophilic anion 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, and an aralkyl group). a carboxylate anion or the like), a sulfonyl quinone imine anion, a bis(alkylsulfonyl) quinone imine anion, a 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 of 3 to 30. Cycloalkyl.

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

The alkyl group, cycloalkyl group and aryl group exemplified may also have a substituent. Specific examples thereof include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3~). 15), an aryl group (preferably having a carbon number of 6 to 14), an alkoxycarbonyl group (preferably having a carbon number of 2 to 7), and an anthracene Base (preferably carbon number 2 to 12), alkoxycarbonyloxy group (preferably carbon number 2 to 7), alkylthio group (preferably carbon number 1 to 15), alkylsulfonyl group (compared Preferably, the carbon number is 1 to 15), the alkylimidosulfonyl group (preferably having a carbon number of 1 to 15), the aryloxysulfonyl group (preferably having a carbon number of 6 to 20), and the alkylaryloxy group. a sulfonyl group (preferably having a carbon number of 7 to 20), a cycloalkylaryloxysulfonyl group (preferably having a carbon number of 10 to 20), an alkoxyalkoxy group (preferably having a carbon number of 5 to 20) And a cycloalkyl alkoxy alkoxy group (preferably having a carbon number of 8 to 20). Further, as the aryl group and the ring structure of each group, an alkyl group (preferably having a carbon number of 1 to 15) may be mentioned as a substituent.

The aralkyl group in the aralkylcarboxylate 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 or a naphthylbutyl group.

Examples of the sulfonyl quinone imine anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl)phosphonium anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. The substituent of the alkyl group may, for example, be a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group or a cycloalkylaryloxysulfonate. The fluorenyl group or the like is preferably a fluorine atom or an alkyl group substituted by a fluorine atom.

Further, the alkyl groups in the bis(alkylsulfonyl) quinone imine anion may be bonded to each other to form a ring structure. Thereby, the acid strength increases.

Examples of the other non-nucleophilic anion include phosphorus fluoride (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), and cesium fluoride (for example, SbF ₆ ^- ).

The non-nucleophilic anion is preferably such that at least the alpha position of the sulfonic acid is substituted by a fluorine atom. An aliphatic sulfonate anion, an aromatic sulfonate anion substituted with a fluorine atom or a fluorine atom-containing group, a bis(alkylsulfonyl) quinone imine anion substituted with a fluorine atom, and an alkyl group substituted by a fluorine atom A tris(alkylsulfonyl)methide anion. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably a carbon number of 4 to 8), a fluorine atom-containing benzenesulfonate anion, and more preferably a nonafluorobutanesulfonate anion or a perfluorooctanesulfonate. Acid anion, pentafluorobenzenesulfonate anion, 3,5-bis(trifluoromethyl)benzenesulfonate anion.

From the viewpoint of acid strength, in order to improve the sensitivity, it is preferred that the pKa of the generated acid is -1 or less.

Further, the non-nucleophilic anion may be an anion represented by the following general formula (AN1) as a preferred embodiment.

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of cases, R ¹ and R ² may be the same or different.

L represents a divalent linking group, and when there are a plurality of L, the L may be the same or different.

A represents a cyclic organic group.

x represents an integer from 1 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

The general formula (AN1) will be described in more detail.

The alkyl group in the alkyl group substituted by the fluorine atom of Xf is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 4. Further, 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. Specific examples of Xf include a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , 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 , of which a fluorine atom or CF _{3 is} preferred. It is especially preferred that the two Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and is preferably a group having 1 to 4 carbon atoms. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent of R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and 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 , wherein CF _{3 is} preferred.

R ¹ and R ^{2 are} preferably a fluorine atom or CF ₃ .

x is preferably from 1 to 10, more preferably from 1 to 5.

y is preferably 0 to 4, more preferably 0.

z is preferably 0 to 5, more preferably 0 to 3.

The divalent linking group of L is not particularly limited, and examples thereof include: -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, cycloalkane The base group, the extended alkenyl group or a linking group in which a plurality of these groups are bonded to each other is preferably a linking group having a total carbon number of 12 or less. Among them, preferred are -COO-, -OCO-, -CO-, -O-, and more preferably -COO-, -OCO-.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (including not only aromatic groups but also aromatic groups). Group) and so on.

The alicyclic group may be a monocyclic ring or a polycyclic ring, preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, a norbornyl group, a tricyclodecylalkyl group or a tetracyclodecylalkyl group. A polycyclic cycloalkyl group such as tetracyclododecyl or adamantyl. Among them, from the viewpoint of suppressing the diffusibility in the film in the post-exposure heating step and improving the Mask Error Enhancement Factor (MEEF), it is preferably a norbornyl group, a tricyclodecyl group, or a tetracyclic ring. An alicyclic group having a large volume structure having a carbon number of 7 or more, such as a decyl group, a tetracyclododecyl group or an adamantyl group.

Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.

Examples of the heterocyclic group include a group derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, a group derived from a furan ring, a thiophene ring or a pyridine ring is preferred.

Further, the cyclic organic group may be a lactone structure, and specific examples thereof include the lactone represented by the formula (LC1-1) to the formula (LC1-17) which the resin (A) described above can have. structure.

The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be any of a straight chain, a branch, and a ring, preferably a carbon number of 1 to 12), and a cycloalkyl group. Any one of a monocyclic, polycyclic, and spiro ring, preferably having a carbon number of 3 to 20), an aryl group (preferably having a carbon number of 6 to 14), a hydroxyl group, an alkoxy group, an ester group, a decylamino group, and an amine group. Carbamate group, urea group, thioether group, sulfonamide group, sulfonate group, and the like. Furthermore, the composition of the ring The organic carbon (which contributes to the formation of the ring) may also be a carbonyl carbon.

The organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may, for example, be an aryl group, an alkyl group or a cycloalkyl group.

Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , preferably at least one is an aryl group, and more preferably all three are aryl groups. The aryl group may be a heteroaryl group such as an anthracene residue or a pyrrole residue, in addition to a phenyl group or a naphthyl group. The alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. More preferably, the alkyl group may be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. More preferably, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group. These groups may also have more substituents. Examples of the substituent include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3~). 15) an aryl group (preferably having a carbon number of 6 to 14), an alkoxycarbonyl group (preferably having a carbon number of 2 to 7), a mercapto group (preferably having a carbon number of 2 to 12), and an alkoxycarbonyloxy group. (preferably, carbon number 2 to 7), etc., but it is not limited to these groups.

In the case where two of R ₂₀₁ to R ₂₀₃ are bonded to form a ring structure, the structure represented by the following formula (A1) is preferred.

In the formula (A1), R ^1a to R ^13a each independently represent a hydrogen atom or a substituent.

In R ^1a to R ^13a , preferably one to three are substituents, and more preferably any one of R ^9a to R ^13a is a substituent.

Za is a single bond or a divalent linking group.

X ^- is the same as Z ^- in the formula (ZI).

Specific examples of the substituent in the case where R ^1a to R ^13a are a substituent include the following groups: a halogen atom, a linear or branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic ring. , cyano, nitro, carboxy, alkoxy, aryloxy, nonyloxy, heterocyclic oxy, decyloxy, amine methoxycarbonyl, alkoxycarbonyloxy, aryloxycarbonyloxy , amine group (including anilino group), ammonium group, mercaptoamine group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, aminesulfonylamino group, alkylsulfonylamine And arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfo, alkylsulfinyl and arylsulfinyl, alkyl sulfonate Mercapto and arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminemethanyl, arylazo and heterocyclic azo, fluorenylene, phosphino, phosphinyl , phosphinyloxy, phosphinylamino, phosphonium, decyl, decyl, ureido, boronic acid (-B(OH) ₂ ), phosphato (-OPO(OH) ₂ ), sulfate groups (sulfato, -OSO ₃ H), other well-known On behalf of the group.

When R ^1a to R ^13a are a substituent, a linear, branched or cyclic alkyl group substituted by a hydroxyl group is preferred.

The divalent linking group of Za may, for example, be an alkyl group, an aryl group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamino group, an ether bond, a thioether bond, an amine group, or a disulfide group. Ether group, -(CH ₂ ) _n -CO-, -(CH ₂ ) _n -SO ₂ -, -CH=CH-, aminocarbonylamino group, aminosulfonylamino group, etc. (n is 1 to 3) Integer).

In addition, a preferred structure of the case where at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is an organic group other than an aryl group is exemplified in paragraph 0046 to paragraph 0848 of JP-A-2004-233661, and Japanese Patent Laid-Open A compound exemplified by the formula (I-1) to the formula (I-70) in the specification of the Japanese Patent Application Publication No. 2003/0224288A1, the disclosure of which is incorporated herein by reference. In the specification, a cationic structure such as a compound exemplified in the formula (IA-1) to the formula (IA-54) and the formula (IB-1) to the formula (IB-24) is used.

In the general formula (ZII) and the general formula (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

An aryl group, an alkyl group, a cycloalkyl group of R ₂₀₄ to R _{207 and} an aryl group or an alkyl group described by an aryl group, an alkyl group or a cycloalkyl group as R ₂₀₁ to R ₂₀₃ in the compound (ZI) described above. The base and the cycloalkyl group are the same.

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. The substituent may also be a substituent which the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI) described above may have.

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

Further, the acid generator may be a compound represented by the following formula (ZIV), formula (ZV) or formula (ZVI).

In the general formula (ZIV) to the general formula (ZVI), Ar ₃ and Ar ₄ each independently represent an aryl group.

R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ include the same groups as the specific examples of the aryl group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the above formula (ZI). group.

Specific examples of the alkyl group and the cycloalkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ include specific examples of the alkyl group and the cycloalkyl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the above formula (ZI). The same group is the case.

The alkylene group of A may, for example, be an alkylene group having 1 to 12 carbon atoms (e.g., methylene, ethyl, propyl, isopropyl, butyl, isobutyl, etc.), The base may be an alkenyl group having 2 to 12 carbon atoms (e.g., a vinyl group, a propenyl group, a butenyl group, etc.), and the aryl group of A may be a aryl group having a carbon number of 6 to 10 (e.g., a phenyl group). , methyl phenyl, naphthyl, etc.).

A preferred example of the acid generator is listed below.

In the present invention, the acid generating compound (B) is preferably irradiated with actinic rays or radiation from the viewpoint of suppressing diffusion of acid generated in the non-exposed portion by exposure and improving the resolution. a compound that generates size than 240Å ³ volume of the acid, more preferably a compound having ³ or more to produce a volume size 300Å acid is thus good to produce a compound of magnitude than 350Å ³ volume of the acid, particularly preferably generated compound volume size than 400Å ³ acids. Among them, the coating solvent or sensitivity in terms of solubility, the volume of preferably 2000Å ³ or less, more preferably 1500Å ³ or less. The value of the volume was obtained by using "WinMOPAC" manufactured by Fujitsu Co., Ltd. That is, the chemical structure of the acid of each case is first input, and then the structure is taken as the initial structure, and the most stable stereo configuration of each acid is determined by using the molecular force field calculation of the MM3 method, and then the most stable stereostructure is The molecular orbital calculation using the PM3 method is performed, whereby the "accessible volume" of each acid can be calculated.

Hereinafter, an acid generator which is particularly preferable in the present invention is exemplified below. Furthermore, a part of the example is given a calculated value of the volume (in units of Å ³ ). Further, the calculated value obtained here is the volume value of the acid in which the proton is bonded to the anion portion.

The acid generators may be used alone or in combination of two or more.

The content of the acid generator in the composition is preferably from 0.1% by mass to 50% by mass, more preferably from 0.5% by mass to 40% by mass, even more preferably from 1% by mass to 30% based on the total solid content of the composition. quality%.

[2] (C) resist solvent (coating solvent)

The solvent which can be used for the preparation of the composition is not particularly limited as long as it is a solvent for dissolving each component, and examples thereof include an alkylene glycol monoalkyl ether carboxylate (Propyleneglycol monomethylether). Acetate, PGMEA, alias 1-methoxy-2-ethoxypropane, etc.), alkyl diol monoalkyl ether (Propyleneglycol monomethylether (PGME; 1-methoxy-2-propanol) ), etc.), alkyl lactate (ethyl lactate, methyl lactate, etc.), cyclic lactone (γ-butyrolactone, etc., preferably having a carbon number of 4 to 10), a chain or cyclic ketone (2) - heptanone, cyclohexanone, etc., preferably having a carbon number of 4 to 10), an alkylene carbonate (ethyl carbonate, propylene carbonate, etc.), an alkyl carboxylate (preferably butyl acetate, etc.) Alkyl acetate), alkyl alkoxyacetate (ethyl ethoxypropionate), and the like. Other solvents which can be used include, for example, the solvent described in <0244> of the specification of the U.S. Patent Application Publication No. 2008/0248425A1.

Among them, an alkylene glycol monoalkyl ether carboxylate and an alkylene glycol monoalkyl ether are preferred.

These solvents may be used singly or in combination of two or more. In the case of mixing two or more kinds, it is preferred to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40.

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

[3] Basic compounds

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a basic compound. The basic compound is preferably a compound which is more basic than phenol. Further, the basic compound is preferably an organic basic compound, more preferably a nitrogen-containing basic compound.

The nitrogen-containing basic compound which can be used is not particularly limited, and for example, it can be used. The compound of the following (1) to (7) is preferably a (4) ammonium salt described later.

(1) a compound represented by the formula (BS-1)

In the general formula (BS-1), R independently represents a hydrogen atom or an organic group. Among them, at least one of the three R is an organic group. The organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group or an aralkyl group.

Description of the compound represented by the above formula (BS-1) (Description of each group, specific examples of the compound represented by the formula (BS-1), etc.) can be referred to Japanese Patent Laid-Open Publication No. 2013-015572 The description of paragraphs 0471 to 0481 is incorporated into the present specification.

(2) Compounds having a nitrogen-containing heterocyclic structure

The nitrogen-containing heterocyclic ring may have aromaticity or may not be aromatic. In addition, it may contain a plurality of nitrogen atoms. Further, it may contain a hetero atom other than nitrogen. Specific examples thereof include a compound having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), a compound having a piperidine structure [N-hydroxyethylpiperidine, and Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) phthalate, etc., compound having a pyridine structure (4- Dimethylaminopyridine, etc.), and a compound having an antipyrine structure (antipyrine and hydroxyantipyrine, etc.).

Examples of preferred compounds having a nitrogen-containing heterocyclic structure include, for example, anthracene, aminopyridine, aminoalkylpyridine, aminopyrrolidine, oxazole, imidazole, pyrazole, pyrazine, pyrimidine, indole, imidazole. Porphyrin, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholine. These groups may also have more substituents.

Preferred examples of the substituent include an amine group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, a decyl group, a decyloxy group, an aryl group, and an aromatic group. Oxyl, nitro, hydroxy and cyano groups.

Particularly preferred compounds having a nitrogen-containing heterocyclic structure include, for example, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-di Ethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2 -Amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N-(2-aminoethyl)piperazine, N -(2-Aminoethyl)piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidylpiperidine, 2-iminopiperidine, 1-( 2-Aminoethyl)pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2-(amine Methyl)-5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine and N-(2-Aminoethyl)morpholine.

In addition, it is also preferred to use a combination of two or more ring structures. Things. Specific examples thereof include 1,5-diazabicyclo[4.3.0]non-5-ene and 1,8-diazabicyclo[5.4.0]-undec-7-ene.

(3) Amine compounds having a phenoxy group

The amine compound having a phenoxy group means a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group may have, for example, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, a decyloxy group, an aryloxy group, or the like. Substituent.

More preferably, the compound has at least one oxygen alkyl chain between the phenoxy group and the nitrogen atom. The number of oxygen-extended alkyl chains in one molecule is preferably from 3 to 9, more preferably from 4 to 6. In the oxygen alkyl chain, it is particularly preferably -CH ₂ CH ₂ O-.

Specific examples include 2-[2-{2-(2,2-dimethoxy-phenoxyethoxy)ethyl}-bis-(2-methoxyethyl)]-amine and US2007 Compound (C1-1) to compound (C3-3) exemplified in paragraph <0066> of the specification of 0224539A1.

The amine compound having a phenoxy group can be obtained, for example, by heating a primary amine or a secondary amine having a phenoxy group and a halogenated alkyl ether, and adding sodium hydroxide, potassium hydroxide and tetraalkylammonium. After the aqueous solution of the strong base is used, the extraction is carried out using an organic solvent such as ethyl acetate or chloroform. Further, an amine compound having a phenoxy group can also be obtained by heating a primary amine or a secondary amine with a halogenated alkyl ether having a phenoxy group at the terminal, and adding sodium hydroxide, potassium hydroxide and tetra After an aqueous solution of a strong base such as an alkylammonium is extracted with an organic solvent such as ethyl acetate or chloroform.

(4) ammonium salt

As the basic compound, an ammonium salt, preferably a quaternary ammonium salt, can also be suitably used.

The cation of the ammonium salt is preferably a tetraalkylammonium cation substituted with an alkyl group having 1 to 18 carbon atoms, more preferably a tetramethylammonium cation, a tetraethylammonium cation, a tetra(n-propyl)ammonium cation, or a tetra( Isopropyl)ammonium cation, tetra(n-butyl)ammonium cation, tetra(n-heptyl)ammonium cation, tetra(n-octyl)ammonium cation, dimethylhexadecyl ammonium cation, benzyltrimethyl cation Etc., preferably a tetra(n-butyl)ammonium cation.

Examples of the anion of the ammonium salt include hydroxides, carboxylates, halides, sulfonates, borates, and phosphates. Among these, a hydroxide or a carboxylate is particularly preferred.

Halides are particularly preferred as chlorides, bromides and iodides.

The sulfonate is particularly preferably an organic sulfonate having 1 to 20 carbon atoms. Examples of the organic sulfonate include an alkylsulfonate having 1 to 20 carbon atoms and an arylsulfonate.

The alkyl group contained in the alkyl sulfonate may also have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, a fluorenyl group, and an aryl group. Specific examples of the alkyl sulfonate include mesylate, ethanesulfonate, butanesulfonate, hexanosulfonate, octanesulfonate, benzylsulfonate, trifluoromethanesulfonate, and pentafluoroethane. Sulfonate and nonafluorobutanesulfonate.

Examples of the aryl group contained in the arylsulfonate include a phenyl group, a naphthyl group, and an anthracenyl group. The aryl groups may also have a substituent. The substituent is preferably, for example, a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms. Specifically, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-hexyl group, and a cyclohexyl group are preferable. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, a decyl group and a decyloxy group.

The carboxylate may be an aliphatic carboxylate or an aromatic carboxylate. For example: acetate, lactate, pyruvate, trifluoroacetate, adamantane carboxylate, hydroxyadamantane carboxylate, benzoate, naphthoate, salicylate, o-benzene The diformate, the phenate or the like is particularly preferably a benzoate, a naphthoate or a phenate, and the like is preferably a benzoate.

In this case, the ammonium salt is preferably tetra(n-butyl)ammonium benzoate or tetrakis(n-butyl)ammonium phenol.

In the case of a hydroxide, the ammonium salt is particularly preferably a tetraalkylammonium hydroxide having a carbon number of 1 to 8 (tetramethylammonium hydroxide and tetraethylammonium hydroxide, tetra-(n-butyl)ammonium hydroxide Tetraalkylammonium hydroxide.

(5) A compound (PA) which has a proton-receptive functional group and which is decomposed by irradiation with actinic rays or radiation to cause a decrease in proton acceptor property, disappearance, or a change from proton acceptor to acidity.

The composition of the present invention may further contain, as a basic compound, a proton-receptive functional group, which is decomposed by irradiation with actinic rays or radiation to cause proton acceptor degradation, disappearance, or proton reception. A compound of a compound which is physically acidic (hereinafter also referred to as a compound (PA)].

A compound (PA) having a proton-receptive functional group and decomposing by irradiation with actinic rays or radiation to cause a decrease in proton acceptor property, or a change from a proton acceptor to an acid may be referred to a Japanese patent. The descriptions of paragraphs 0379 to 4025 of the Japanese Patent Application Laid-Open No. 2012-32762 (the <RTIgt;

In the composition of the present invention, the compounding ratio of the compound (PA) in the entire composition is preferably from 0.1% by mass to 10% by mass based on the total solid content, more preferably from 1% by mass to 8% by mass.

(6) bismuth compound

The composition of the present invention may further contain a ruthenium compound.

The ruthenium compound can be incorporated by reference to the description of paragraph 0374 to paragraph 0378 of the Japanese Patent Application Laid-Open No. 2012-32762 (corresponding to <0382> to <0385> of the specification of the corresponding US Patent Application Publication No. 2012/0003590). To this manual.

(7) a low molecular compound having a nitrogen atom and having a group desorbed by the action of an acid

The composition of the present invention may contain a low molecular compound having a nitrogen atom and having a group which is desorbed by the action of an acid (hereinafter also referred to as "low molecular compound (D)" or "compound (D)"). The low molecular compound (D) is preferably basic after being detached from the group which is desorbed by the action of an acid.

The low molecular compound (D) can be referred to in the specification by referring to the description of paragraphs 0324 to 0337 of JP-A-2012-133331.

In the present invention, the low molecular compound (D) may be used alone or in combination of two or more.

The composition of the present invention may contain the low molecular compound (D) or the low molecular compound (D), and in the case of the low molecular compound (D), the total solid content of the composition in combination with the basic compound The content of the compound (D) is usually 0.001% by mass to 20% by mass, preferably 0.001% by mass to 10% by mass. The amount % is more preferably 0.01% by mass to 5% by mass.

In addition, the basic compound which can be used in the composition of the present invention is exemplified by a compound synthesized in the examples of JP-A-2002-363146, and in paragraph 0108 of JP-A-2007-298569. The compound or the like described.

A photosensitive basic compound can also be used as the basic compound. As the photosensitive basic compound, for example, Japanese Patent Laid-Open Publication No. 2003-524799 and "J. Photopolym. Sci & Tech." (Vol. 8, P. 543-553 (1995) can be used. )) The compound described in the above.

The molecular weight of the basic compound is usually from 100 to 1,500, preferably from 150 to 1300, more preferably from 200 to 1,000.

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

When the composition of the present invention contains a basic compound, the content thereof is preferably from 0.01% by mass to 10.0% by mass, more preferably from 0.1% by mass to 8.0% by mass, based on the total solid content of the composition. It is 0.2% by mass to 5.0% by mass.

The molar ratio of the basic compound to the acid generator is preferably from 0.01 to 10, more preferably from 0.05 to 5, and even more preferably from 0.1 to 3. If the molar ratio is excessively increased, the sensitivity and/or resolution may be lowered. If the molar ratio is excessively reduced, the pattern may become thinner between exposure and heating (post-baking). More preferably 0.05 to 5, and thus preferably 0.1 to 3. Further, the acid generator in the molar ratio may be further contained in the repeating unit represented by the formula (5) of the resin and the resin. The total amount of the acid generator is based on the total amount.

[4] Compounds which are decomposed by the action of an acid to generate an acid

The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention may further contain one or two or more compounds which are decomposed by the action of an acid to generate an acid. The acid produced by the compound which is decomposed by the action of an acid to generate an acid is preferably a sulfonic acid, a methamic acid or a quinone.

Hereinafter, examples of the compound which can be decomposed by the action of an acid to generate an acid which can be used in the present invention are shown, but are not limited to these examples.

The compound which is decomposed by the action of an acid to generate an acid may be used alone or in combination of two or more.

Further, according to the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention The content of the compound which decomposes by the action of an acid to generate an acid is preferably from 0.1% by mass to 40% by mass, more preferably from 0.5% by mass to 30% by mass, even more preferably from 1.0% by mass to 20% based on the total solid content. quality%.

[5] Hydrophobic resin (HR)

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a hydrophobic resin (HR) different from the resin (A).

The hydrophobic resin is preferably designed to be biased toward the surface of the resist film. Unlike the surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and it does not help to uniformly mix the polar substance/nonpolar substance. .

The effect of adding a hydrophobic resin is to control the static/dynamic contact angle of the surface of the resist film with respect to water, to suppress out gas, and the like.

In view of the fact that the hydrophobic resin is present on the surface of the film, the hydrophobic resin preferably has at least one of a "fluorine atom", a "deuterium atom", and a "CH ₃ partial structure contained in a side chain portion of the resin". There are two or more.

When the hydrophobic resin contains a fluorine atom and/or a ruthenium atom, the fluorine atom and/or the ruthenium atom in the hydrophobic resin 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 is preferably a resin having a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group or a fluorine atom-containing aryl group as a fluorine atom-containing partial structure.

The fluorine atom-containing alkyl group (preferably having a carbon number of 1 to 10, more preferably a carbon number of 1 to 4) is a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may further have fluorine. A substituent other than an atom.

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

The aryl group of the fluorine atom may be a group 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 may further have a substituent other than a fluorine atom.

Examples of the repeating unit of the fluorine-containing atom or the halogen atom may be the repeating unit exemplified in paragraph 0519 of US2012/0251948A1.

Further, as described above, the hydrophobic resin preferably also has a CH ₃ moiety structure in the side chain portion.

Here, the structure of the side chain portion ₃ partially hydrophobic resin contained in the CH (hereinafter also referred to as "partial structure a side chain CH _3"), the structure comprising _three parts ethyl, propyl and the like has CH.

On the other hand, a methyl group directly bonded to a main chain of a hydrophobic resin (for example, an α-methyl group having a repeating unit of a methacrylic acid structure) is present on the surface due to the influence of the main chain on the surface of the hydrophobic resin. It is considered to be not included in the CH ₃ partial structure of the present invention.

More specifically, the hydrophobic resin contains, for example, a repeating unit represented by the following formula (M), and a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, and R ₁₁ to R ₁₄ In the case where CH _{3 is} "self", the CH _{3 is} not included in the CH ₃ moiety structure contained in the side chain portion of the present invention.

On the other hand, the CH ₃ partial structure existing from the CC main chain via any atom is considered to correspond to the CH ₃ partial structure of the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is considered to have "one" CH ₃ partial structure of the present invention.

In the above formula (M), R ₁₁ to R ₁₄ each independently represent a side chain moiety.

R ₁₁ to R _{14 in the} side chain moiety may, for example, be a hydrogen atom, a monovalent organic group or the like.

Examples of the monovalent organic group of R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamine. The carbonyl group, the arylaminocarbonyl group and the like may further have a substituent.

The hydrophobic resin is preferably a resin containing a repeating unit having a CH ₃ moiety structure in a side chain portion, and such a repeating unit is more preferably a repeating unit represented by the following formula (II) and a formula (III) below At least one of the repeating units represented is a repeating unit (x).

Hereinafter, the repeating unit represented by the formula (II) will be described in detail.

In the above formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₂ represents an organic group having one or more CH ₃ partial structures and being stable to an acid. Here, more specifically, the acid-stable organic group is preferably an organic group other than the "acid-decomposable group" described in the resin (A).

The alkyl group of X _b1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a methyl group is preferable.

X _{b1 is} preferably a hydrogen atom or a methyl group.

R ₂ may, for example, be an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group having one or more CH ₃ partial structures. The cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.

R _{2 is} preferably an alkyl group having one or more CH ₃ moiety structures or an alkyl group-substituted cycloalkyl group.

The organic group having one or more CH ₃ partial structures and having an acid stability of R ₂ preferably has two or more and ten or less CH ₃ partial structures, more preferably two or more and eight or less. CH ₃ part structure.

Preferred specific examples of the repeating unit represented by the formula (II) are listed below. Furthermore, the invention is not limited thereto.

The repeating unit represented by the formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, it is preferably a group having a polar group which is decomposed by an action of an acid to generate a polar group. Repeat unit of the group.

Hereinafter, the repeating unit represented by the formula (III) will be described in detail.

In the above formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₃ represents an organic group having one or more CH ₃ partial structures and being stable to an acid, and n represents 1 to 5; Integer.

The alkyl group of X _b2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a hydrogen atom is preferred.

X _{b2 is} preferably a hydrogen atom.

R ₃ is an organic group which is stable to an acid, and more specifically, it is preferably an organic group which does not have the "acid-decomposable group" described in the above resin (A).

R ₃ may, for example, be an alkyl group having one or more CH ₃ partial structures.

The organic group having one or more CH ₃ partial structures and having an acid stability of R ₃ preferably has one or more and ten or less CH ₃ partial structures, and more preferably one or more and eight or less CHs. _{The three-} part structure preferably further has one or more and four or less CH ₃ partial structures.

n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and more preferably 1 or 2.

Preferred specific examples of the repeating unit represented by the formula (III) are listed below. Furthermore, the invention is not limited thereto.

The repeating unit represented by the formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, preferably a group which does not have a polar group by decomposition by an action of an acid. Repeat unit.

In the case where the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, and further, especially in the case of not containing a fluorine atom and a ruthenium atom, with respect to all the repeating units of the hydrophobic resin, the formula (II) The content of at least one repeating unit (x) in the repeating unit and the repeating unit represented by the formula (III) is preferably 90 mol% or more, more preferably 95 mol% or more. The content is usually 100 mol% or less based on all the repeating units of the hydrophobic resin.

The hydrophobic resin contains at least one repeating unit represented by the formula (II) and at least one repeating unit (x) represented by the formula (III), with respect to all the repeating units of the hydrophobic resin, at 90 mol% or more, Thereby, the surface free energy of the hydrophobic resin is increased. As a result, the hydrophobic resin tends to be biased toward the surface of the resist film.

Further, when the hydrophobic resin contains (i) a fluorine atom and/or a ruthenium atom, and (ii) a CH ₃ moiety structure in a side chain moiety, it may have at least one selected from the following (x). a group in the group of ~(z).

(x) an acid group, (y) a group having a lactone structure, an acid anhydride group or a phosphonium imino group, (z) a group which is decomposed by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, and a sulfonic acid group. Acid group, sulfonylamino group, sulfonyl sulfoximine, (alkylsulfonyl) (alkylcarbonyl) methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenylene, double (alkylcarbonyl)methylene, bis(alkylcarbonyl)indenylene, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)indolylene, tris(alkylcarbonyl) a methylene group, a tris(alkylsulfonyl)methylene group, and the like.

Preferred acid groups include a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonimide group, and a bis(alkylcarbonyl)methylene group.

The repeating unit having an acid group (x) may be a repeating unit derived from a repeating unit of acrylic acid or methacrylic acid directly bonded to a resin main chain, or an acid group bonded to a resin main chain via a linking group. The repeating unit or the like may be further introduced into the end of the polymer chain by using a polymerization initiator or a chain transfer agent having an acid group during polymerization, and any of them is preferred. The repeating unit having an acid group (x) may further contain at least one of a fluorine atom and a germanium atom.

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

Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

The group having a lactone structure, an acid anhydride group or a ruthenium iodide group (y) is particularly preferably a group having a lactone structure.

The repeating unit containing such a group may be, for example, a repeating unit derived from a repeating unit derived from an acrylate or a methacrylate, and the group directly bonded to the resin main chain. Alternatively, the repeating unit may be a repeating unit in which the group is bonded to the resin main chain via a linking group. Alternatively, the repeating unit may be introduced to the end of the resin by using a polymerization initiator or a chain transfer agent having the group at the time of polymerization.

The repeating unit containing a group having a lactone structure may, for example, be the same repeating unit as the repeating unit having a lactone structure described above in the item of the resin (A).

The content of the repeating unit containing a group having a lactone structure, an acid anhydride group or an acid sulfonium imino group is preferably from 1 mol% to 100 mol%, more preferably from 3 mol% to 98 mol, based on all the repeating units in the hydrophobic resin. %, and further preferably from 5 mol% to 95 mol%.

The repeating unit of the group (z) having a group which is decomposed by the action of an acid in the hydrophobic resin may be the same repeating unit as the repeating unit having an acid-decomposable group exemplified in the resin (A). The weight of the group (z) having a decomposition by the action of an acid The complex unit may have at least one of a fluorine atom and a germanium atom. The content of the repeating unit having a group (z) which is decomposed by the action of an acid in the hydrophobic resin is preferably from 1 mol% to 80 mol%, more preferably 10 mol%, based on all the repeating units in the hydrophobic resin. 80 mol%, and further preferably 20 mol% to 60 mol%.

When the hydrophobic resin contains a fluorine atom, the content of the fluorine atom is preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 80% by mass based on the weight average molecular weight of the hydrophobic resin. Further, in all the repeating units contained in the hydrophobic resin, the repeating unit of the fluorine atom is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%.

When the hydrophobic resin contains a ruthenium atom, the content of the ruthenium atom is preferably from 2% by mass to 50% by mass, and more preferably from 2% by mass to 30% by mass based on the weight average molecular weight of the hydrophobic resin. Further, in all the repeating units contained in the hydrophobic resin, the repeating unit containing a halogen atom is preferably from 10 mol% to 100 mol%, more preferably from 20 mol% to 100 mol%.

On the other hand, in particular, in the case where the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, the hydrophobic resin is also preferably in a form substantially free of fluorine atoms and germanium atoms, in which case, specifically, The content of the repeating unit containing a fluorine atom or a ruthenium atom is preferably 5 mol% or less, more preferably 3 mol% or less, further preferably 1 mol% or less, and desirably 0 mol%, based on all the repeating units in the hydrophobic resin. That is, there are no fluorine atoms and germanium atoms. Further, the hydrophobic resin is preferably substantially composed only of repeating units composed of only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom. More specifically, in all the repeating units of the hydrophobic resin, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is preferably 95 mol% or more, more preferably It is 97 mol% or more, and further preferably 99 mol% or more, and desirably 100 mol%.

The standard polystyrene-equivalent weight average molecular weight of the hydrophobic resin is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, and still more preferably from 2,000 to 15,000.

Further, the hydrophobic resin may be used alone or in combination of two or more.

The content of the hydrophobic resin in the composition is preferably from 0.01% by mass to 10% by mass, more preferably from 0.05% by mass to 8% by mass, even more preferably 0.1% by mass, based on the total solid content of the composition of the present invention. ~7 mass%.

The hydrophobic resin is of course less rare in metal or the like, and preferably has a residual monomer or oligomer component of 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass, and still more preferably 0.05% by mass to 1% by mass. quality%. Thereby, a composition which does not change with time, such as a foreign substance, a sensitivity, etc., can be obtained. Further, the molecular weight distribution (Mw/Mn, also referred to as dispersity) is preferably in the range of 1 to 5, in terms of resolution, resist shape, side wall of the resist pattern, roughness, and the like, and more preferably The range of 1~3 is better than the range of 1~2.

The hydrophobic resin can be used in various commercial products, and can also be synthesized by a usual method (for example, radical polymerization). For example, a general synthesis method may be exemplified by an overall polymerization method in which a monomer species and an initiator are dissolved in a solvent and heated to carry out polymerization; in a heating solvent, a monomer species is added dropwise over 1 hour to 10 hours. Drop of solution of the initiator A polymerization method or the like is preferred, and a dropwise addition polymerization method is preferred.

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 in the resin (A), and in the synthesis of the hydrophobic resin, the reaction concentration is preferably 30 mass. %~50% by mass.

Further, in addition to the above, the hydrophobic resin can be preferably used as described in JP-A-2011-248019, JP-A-2010-175859, and JP-A-2012-032544.

[6] surfactants

The composition of the present invention may further contain a surfactant. By using a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used, a pattern having excellent sensitivity and resolution, good adhesion, and less development defects can be formed.

It is especially preferable to use a fluorine-based and/or a lanthanoid surfactant as the surfactant.

Examples of the fluorine-based and/or lanthanoid surfactants include the surfactants described in <0276> of the specification of U.S. Patent Application Publication No. 2008/0248425. Also available: Eftop EF301 or Eftop EF303 (made by New Akita Chemicals Co., Ltd.); Fluorad FC430, Fluorad 431 or Frode ( Fluorad) 4430 (manufactured by Sumitomo 3M); Megafac F171, Megafac F173, Megafac F176, Megafac F189, Megafac F113, Meijiafa ( Megafac) F110, Megafac F177, Megafac F120 or Megafac R08 (made by DiCai (DIC)); Surflon S-382, Surflon SC101, Surflon 102, Surflon 103, Surflon 104, Surflon 105 or Surflon 106 (made by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by East Asian Synthetic Chemicals Co., Ltd.); Surflon S-393 (made by Seimi Chemical); Eftop EF121, Eftop EF122A, Eftop EF122B, Eftop RF122C, Eftop EF125M, Eftop EF135M, Eftop EF351, Eftop EF352, Eftop EF801, Eftop EF802 or Eftop EF601 (manufactured by Jemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos). Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a lanthanoid surfactant.

Further, in addition to the known surfactants as described above, the surfactant may also be used by a short-chain polymerization method (also referred to as a short-chain polymer method) or an oligomerization method (also referred to as an oligomer method). The fluoroaliphatic compound produced is synthesized. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can also be used as a surfactant. The fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

The polymer having a fluoroaliphatic group is preferably a single having a fluoroaliphatic group. The copolymer of at least one of (poly(oxyalkylene)) acrylate and (poly(oxyalkylene)) methacrylate may be distributed irregularly or may be block copolymerized.

Examples of the poly(oxyalkylene) group include a poly(oxyethylidene) group, a poly(oxypropyl) group, and a poly(oxybutylene) group. Further, it may be in the same chain as poly(oxygen extension ethyl, block extension of oxygen-extended propyl group and oxygen-extended ethyl group) and poly(block-connecting body of oxygen-extended ethyl group and oxygen-extended propyl group). A unit having an alkyl group having a different chain length.

Further, the copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene)) acrylate or methacrylate may be a monomer having two or more different fluoroaliphatic groups and different A ternary or higher copolymer obtained by simultaneously copolymerizing two or more kinds of (poly(oxyalkylene)) acrylate or methacrylate.

For example, commercially available surfactants include, for example, Megafac F178, Megafac F-470, Megafac F-473, Megafac F-475, and Megafac. F-476 and Megafac F-472 (manufactured by Di Aisheng (DIC) Co., Ltd.). Further, a copolymer of acrylate or methacrylate having a C ₆ F ₁₃ group and (poly(oxyalkylene)) acrylate or methacrylate, an acrylate having a C ₆ F ₁₃ group or a group can be cited. Copolymer of acrylate and (poly(oxyethylidene)) acrylate or methacrylate with (poly(oxypropyl)) acrylate or methacrylate, acrylate having C ₈ F ₁₇ group Or a copolymer of methacrylate with (poly(oxyalkylene)) acrylate or methacrylate, and an acrylate or methacrylate having a C ₈ F ₁₇ group with (poly(oxyethyl) a copolymer of acrylate or methacrylate with (poly(oxypropyl)) acrylate or methacrylate, and the like.

In addition, U.S. Patent Application Publication No. 2008/0248425 can also be used. A surfactant other than fluorine and/or lanthanum described in <0280> of the specification.

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

When the composition of the present invention contains a surfactant, the content thereof is preferably from 0% by mass to 2% by mass based on the total solid content of the composition, more preferably from 0.0001% by mass to 2% by mass, and further preferably It is 0.0005 mass% to 1 mass%.

[7]Other additives

The composition of the present invention may contain, in addition to the components described above, a carboxylic acid or a carboxylic acid strontium salt, and "Proceeding of SPIE (The International Society for Optical Engineering)" (2724, 355). (1996)) A dissolution inhibiting compound having a molecular weight of 3,000 or less, a dye, a plasticizer, a photosensitizer, a light absorbing agent, an antioxidant, and the like.

In particular, carboxylic acids are preferably used to improve performance. The carboxylic acid is preferably an aromatic carboxylic acid such as benzoic acid or naphthoic acid.

The content of the carboxylic acid in the total solid content concentration of the composition is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, and still more preferably 0.01% by mass to 3% by mass.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used in a film thickness of 10 nm to 250 nm, more preferably in a film thickness of 20 nm to 200 nm, from the viewpoint of improving the resolution. Use at 30nm~100nm. By setting the solid content concentration in the composition to an appropriate range and having an appropriate viscosity, the coating property and the film forming property can be improved, and the film thickness can be set.

Solid component of the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention The concentration is usually 1.0% by mass to 10% by mass, preferably 2.0% by mass to 5.7% by mass, more preferably 2.0% by mass to 5.3% by mass. By setting the solid content concentration to the above range, the resist solution can be uniformly applied onto the substrate, and a resist pattern having excellent line width roughness can be formed. Although the reason is not clear, it is considered that the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, whereby aggregation of a raw material, particularly a photoacid generator, in the resist solution can be suppressed. As a result, a uniform resist film can be formed.

The solid content concentration refers to the mass percentage of the mass of the other resist component excluding the solvent to the total mass of the sensitizing ray-sensitive or radiation-sensitive resin composition.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is prepared by dissolving the component in a predetermined organic solvent, preferably in the mixed solvent, and filtering the filter, and then applying it to a predetermined support (substrate). ) use it. The filter used for the filtration of the filter is preferably a filter 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. . When the filter is filtered, for example, it can be circulated and filtered as in the case of JP-A-2002-62667, and a plurality of filters can be filtered in series or in parallel. Alternatively, the composition can be filtered multiple times. Further, the composition may be subjected to a degassing treatment or the like before and after the filter is filtered.

<resist film>

The present invention also relates to a sensitized ray-sensitive or radiation-sensitive film formed using the composition (composition (i) or composition (ii)) of the present invention (hereinafter also It is called a resist film).

<pattern forming method>

The pattern forming method of the present invention is a pattern forming method including at least the following steps: (A) a step of forming a film (resist film) using the composition (i) or the composition (ii) described above; (B) a step of exposing the film; and (C) a step of removing the exposed portion of the exposed film using an alkaline developing solution to form a pattern (alkali developing step).

Further, the pattern forming method of the present invention is a pattern forming method including at least the following steps: (A) a step of forming a film (resist film) using the composition (i) or the composition (ii) described above; (B) a step of exposing the film; and (C) a step of removing the exposed portion of the exposed film using a developing solution containing an organic solvent to form a pattern (organic solvent developing step).

The exposure in the step (B) may also be a liquid immersion exposure.

The pattern forming method of the present invention preferably comprises (D) a heating step after the (B) exposure step.

In the pattern forming method of the present invention, when the developing solution in the step (C) is a developing solution containing an organic solvent, it may further include (E) a step of performing development using an alkaline developing solution, and on the other hand, The developing solution in the step (C) is alkaline development In the case of a liquid, it may further include (E) a step of developing using a developing solution containing an organic solvent.

In the present invention, the portion having weak exposure intensity is removed by the organic solvent developing step, and the portion having high exposure intensity is also removed by performing the alkali developing step. By performing the multiple development process in which the development is performed as many times as described above, pattern formation can be performed without dissolving the area of the intermediate exposure intensity, so that a more fine pattern is formed (Japanese Patent Laid-Open No. 2008-292975) Paragraph <0077> the same mechanism).

In the pattern forming method of the present invention, the order of the alkali developing step and the organic solvent developing step is not particularly limited, and it is more preferred to perform alkali development before the organic solvent developing step.

The pattern forming method of the present invention may include a plurality of (B) exposure steps.

The pattern forming method of the present invention may include a plurality of (D) heating steps.

The resist film formed of the composition (i) or the composition (ii) is preferably formed on the substrate.

In the pattern forming method of the present invention, the step of forming a film on the substrate using the composition (i) or the composition (ii), the step of exposing the film, and the developing step can be carried out by a generally known method.

The composition (i) or the composition (ii) is, for example, a substrate (for example, bismuth/cerium oxide) which is applied to a production of a precision integrated circuit element, an imprint mold, or the like using a spinner, a coater, or the like. Coated, tantalum nitride, and chromium-deposited quartz substrate, etc.). Thereafter, it can be dried to form a resist film.

An anti-reflection film may be preliminarily coated on the substrate before the resist film is formed.

As the antireflection film, any of an inorganic film type such as titanium, titanium oxide, titanium nitride, chromium oxide, carbon, or amorphous germanium, and an organic film type containing a light absorbing agent and a polymer material can be used. In addition, the organic anti-reflection film can also be used: DUV30 series or DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5, etc. manufactured by Shipley. A commercially available organic antireflective film.

It is also preferred to include a pre-heating step (Prebake (PB)) after film formation and before the exposure step. In addition, it is also preferred to include a post-exposure heating step (Post Exposure Bake (PEB)) after the exposure step and before the development step.

Regarding the heating temperature, it is preferred that both PB and PEB are carried out at 70 ° C to 120 ° C, more preferably at 80 ° C to 110 ° C.

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

Heating can be performed by a mechanism provided by a normal exposure ‧ developing machine, or by using a hot plate or the like.

The reaction of the exposed portion is promoted by baking to improve the sensitivity or pattern outline.

In addition, it is also preferred to include a heating step (Post Bake) after the rinsing step. The developer and the eluent remaining between the patterns and the inside of the pattern are removed by baking.

Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, and electron beam. More preferably, the actinic rays or radiation have a wavelength of, for example, 250 nm or less, particularly 220 nm or less. Examples of such actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, and electron beam. Preferred actinic rays or radiations include, for example, KrF excimer lasers, ArF excimer lasers, electron beams, X-rays, and EUV light. More preferred are electron beam, X-ray and EUV light.

The substrate on which the film is formed in the present invention is not particularly limited, and an inorganic substrate such as ruthenium, SiN or SiO ₂ , a coated inorganic substrate such as spin-on-glass (SOG), or the like can be used, and an integrated circuit (Integrated) can be used. A semiconductor manufacturing step such as a circuit or an IC, a manufacturing step of a circuit board such as a liquid crystal or a thermal head, and a substrate generally used in a lithography step of another photolithography process. Further, an organic anti-reflection film may be formed between the film and the substrate as needed.

In the case where the pattern forming method of the present invention has a step of performing development using an alkaline developer, the alkaline developer may be, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, or ammonia. Such as inorganic bases, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine and three Alcoholamines such as ethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraammonium hydroxide, tetrahexylammonium hydroxide, hydrogen hydroxide Tetraalkylammonium hydroxide, such as octyl ammonium, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriammonium hydroxide, dibutyldipentylammonium hydroxide, or the like Trimethylphenylammonium, hydrogen An alkaline aqueous solution such as a quaternary ammonium salt such as trimethylbenzylammonium or triethylbenzylammonium hydroxide; or a cyclic amine such as pyrrole or piperidine.

Further, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution to be used.

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

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

Particularly preferred is a 2.38 mass% aqueous solution of tetramethylammonium hydroxide.

The eluent used in the rinsing treatment after alkali development is pure water, and an appropriate amount of a surfactant may be added and used.

Further, after the development treatment or the rinsing treatment, the treatment for removing the developer or eluent adhering to the pattern by the supercritical fluid may be performed.

In the case where the pattern forming method of the present invention includes a step of performing development using a developing solution containing an organic solvent, the developing solution (organic developing solution) in this step may be a ketone solvent, an ester solvent, or an alcohol solvent. A polar solvent such as a guanamine solvent or an ether solvent or a hydrocarbon solvent.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, and 1-hexanone. , 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetonyl acetone, acetone acetone, violet Ionone, diacetone alcohol, acetyl carbinol, acetophenone, methylnaphthyl ketone, isophorone, propyl carbonate, and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, and B. Isopropyl acrylate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Ester, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, and the like.

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, 4-methyl-2-pentanol, tert-butanol, isobutanol, and n-hexanol. An alcohol such as n-heptanol, n-octanol or n-nonanol, or a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether or ethylene glycol A glycol ether solvent such as monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol.

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

The guanamine-based solvent can be, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine, 1 , 3-dimethyl-2-imidazolidinone and the like.

Examples of the hydrocarbon-based solvent include an aromatic hydrocarbon solvent such as toluene or xylene, and an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

The solvent may be mixed in a plurality of types, or may be used in combination with a solvent or water other than the above. In order to fully exert the effects of the present invention, it is preferred that the total moisture content of the developer is less than 10% by mass, and more preferably substantially no moisture.

In other words, the amount of the organic solvent to be 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 based on 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 a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and still more preferably 2 kPa or less at 20 °C. By setting the vapor pressure of the organic developing solution to 5 kPa or less, the evaporation of the developing solution on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved, resulting in uniform size in the wafer surface. Sex has changed.

Specific examples of the developer having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), and 4-glycol. Ketone solvents such as ketone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, Isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate , ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, lactate B Ester ester solvent such as ester, butyl lactate or propyl lactate, n-propanol, isopropanol, n-butanol, second butanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol An alcohol solvent such as n-nonanol, a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether or propylene glycol monomethyl a glycol ether solvent such as ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol, an ether solvent such as tetrahydrofuran, N-A Amidoxime solvent such as benzyl-2-pyrrolidone, N,N-dimethylacetamide or N,N-dimethylformamide, an aromatic hydrocarbon solvent such as toluene or xylene, octane or oxime An aliphatic hydrocarbon solvent such as an alkane.

Specific examples of the developer having a vapor pressure of 2 kPa or less which is a particularly preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, and 4-heptanone. a ketone solvent such as 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone or phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3- An ester solvent such as methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate or propyl lactate, n-butanol, second butanol, third butanol, isobutanol, n-hexanol An alcohol solvent such as n-heptanol, n-octanol or n-nonanol, a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether or B Glycol ether solvent such as diol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol, N-methyl-2-pyrrolidone, N , N-dimethylacetamide, N,N-dimethylformamide, etc. , Xylene and the like aromatic hydrocarbon solvents, octane, decane and other aliphatic hydrocarbon solvents.

The organic developer may also contain a basic compound. Specific examples and preferred examples of the basic compound which may be contained in the developer used in the present invention are the same as those of the basic compound which may be contained in the above-mentioned photosensitive ray-sensitive or radiation-sensitive resin composition.

In the organic developer, an appropriate amount of interfacial activity may be added as needed. Agent.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. Examples of the fluorine-based and/or lanthanide-based surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and Japan. JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-H08-62834, JP-A No. 8-62834, and JP-A-9-54432 Japanese Patent Laid-Open No. Hei 9-5988, U.S. Patent No. 5,405, 720, U.S. Patent No. 5,360, 692, U.S. Patent No. 5,529, 881, U.S. Patent No. 5,296,330, U.S. Patent No. 5,436,098, U.S. Patent No. 5,576,143 The surfactant described in the specification, the specification of U.S. Patent No. 5,294,511, and the specification of U.S. Patent No. 5,824,451 is preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, and a fluorine-based surfactant or a quinone-based surfactant is more preferably used.

The amount of the surfactant used is preferably from 0% by mass to 2% by mass, more preferably from 0.0001% by mass to 2% by mass, even more preferably from 0.0005% by mass to 1% by mass, based on the total amount of the developer.

The developing method can be applied, for example, to a method of immersing a substrate in a bath filled with a developing solution for a certain period of time (dipping method), and a method of developing the developing solution by stacking the developing solution on the surface of the substrate and holding it for a certain period of time. Puddle method; a method of spraying a developer onto a substrate surface (spray method); scanning at a certain speed on one side A method (dynamic distribution method) in which a developing solution is continuously ejected onto a substrate that rotates at a constant speed while the film liquid ejects the nozzle.

In the case where the various developing methods include the step of ejecting the developing solution from the developing nozzle of the developing device to the resist film, the ejection pressure of the ejected developing solution (the flow rate per unit area of the ejected developing solution) is preferably It is 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, and still more preferably 1 mL/sec/mm ² or less. The flow rate does not particularly have a lower limit, and is preferably 0.2 mL/sec/mm ² or more in consideration of a throughput.

By setting the discharge pressure of the discharged developing solution to the above range, the defects of the pattern derived from the resist residue after development can be remarkably reduced.

Although the detailed mechanism is not certain, it is considered to be because the pressure applied to the resist film by the developer is reduced by setting the discharge pressure to the above range, and the resist film ‧ resist pattern can be suppressed A situation that is inadvertently cut or destroyed.

Further, the discharge pressure (mL/sec/mm ² ) of the developer is a value at the exit of the developing nozzle in the developing device.

The method of adjusting the discharge pressure of the developing solution is, for example, a method of adjusting the discharge pressure by a pump or the like, or a method of adjusting the pressure by adjusting the pressure from the supply of a tank, thereby changing the discharge pressure.

Further, after the step of performing development using a developing solution containing an organic solvent, the step of stopping the development while replacing the organic developing solution with another solvent may be carried out.

After the step of developing using a developer containing an organic solvent, The step of washing with an eluent may be included, and the step of washing with an eluent may not be included in terms of the amount of processing (productivity), the amount of eluent used, and the like.

The eluent used in the rinsing step after the step of performing development using the developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a usual organic solvent can be used. The eluent preferably contains a group selected from the group consisting of a hydrocarbon solvent (preferably a decane), a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. At least one organic solvent eluent.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent are the same as those exemplified in the developer containing the organic solvent.

After the step of performing development using a developer containing an organic solvent, it is more preferred to use at least one organic solvent containing a group selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. The step of washing the eluent, and preferably the step of washing the eluent containing the alcohol solvent or the ester solvent, and preferably the step of washing with the eluent containing the monohydric alcohol, is preferably carried out. The step of washing with an eluent containing a monohydric alcohol having 5 or more carbon atoms is used.

Here, the monohydric alcohol used in the elution step may, for example, be a linear, branched or cyclic monohydric alcohol, and specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, Tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2 - heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, etc., and a preferred monohydric alcohol having a carbon number of 5 or more can be used: 1-hexanol, 2- Hexanol, 4- Methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

The respective components may be mixed in a plurality of kinds, and may be used in combination with an organic solvent other than the above.

The water content in the eluent is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The vapor pressure of the eluent used after the step of performing development using the developing solution containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more at 20 ° C. , 3kPa or less. By setting the vapor pressure of the eluent to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling due to the penetration of the eluent is suppressed, and the dimensional uniformity in the wafer surface is improved. It is getting better.

An appropriate amount of a surfactant may be added to the eluent for use.

In the rinsing step, the wafer subjected to development using a developing solution containing an organic solvent is subjected to a cleaning treatment using the organic solvent-containing eluent. The method of the cleaning treatment is not particularly limited, and for example, a method of continuously ejecting the eluent onto a substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a tank filled with the eluent for a certain period of time can be applied. The method (dipping method), the method of spraying the eluent onto the surface of the substrate (spray method), etc., wherein the cleaning treatment is preferably performed by a spin coating method, and after the cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm. The wash solution is removed from the substrate. Further, it is also preferred to carry out a heating step (Post Bake) after the rinsing step. Development that remains between the patterns and inside the pattern by baking Remove liquid and eluent. The heating step after the rinsing step is usually carried out at 40 ° C to 160 ° C, preferably 70 ° C to 95 ° C for usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

In addition, the embossing mold can be produced by using the composition of the present invention. For details, for example, Japanese Patent No. 4109085 and Japanese Patent Laid-Open No. 2008-162101.

The pattern forming method of the present invention can also be used for the formation of a guide pattern of Directed Self-Assembly (DSA) (for example, see "ACS Nano", Vol. 4, No. 8, page 4815 - 4823 pages).

In addition, the resist pattern formed by the above-described method can be used, for example, as a core material (core portion) of the spacer process disclosed in Japanese Laid-Open Patent Publication No. Hei No. 3-270227 and Japanese Patent Laid-Open No. Hei No. 2013-164509. .

Further, the present invention relates to a method of manufacturing an electronic component including the pattern forming method of the present invention, and an electronic component manufactured by the method.

The electronic component of the present invention is preferably mounted on an electric and electronic device (home appliance, office automation (OA), media related equipment, optical equipment, communication equipment, etc.).

The pattern forming method of the present invention can be preferably used for the fabrication of semiconductor microcircuits such as the manufacture of ultra LSI or high capacity microchips. In addition, when a semiconductor thin circuit is produced, a resist film formed with a pattern is used for circuit formation or etching, and finally the remaining resist film portion is removed by a solvent or the like, so that it is used for a printed circuit board or the like. In the final product such as a microchip, a resist film derived from the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention does not remain.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

<Synthesis Example 1: Synthesis of Resin (P-1)>

5.0 g of the compound represented by the following formula (1), 14.3 g of the compound represented by the following formula (2), 25.0 g of a 50% by mass cyclohexanone solution of p-hydroxystyrene, and a polymerization initiator V-601 ( 4.0 g of Wako Pure Chemical Industries Co., Ltd. was dissolved in 76.3 g of cyclohexanone. To the reaction vessel was added 15.3 g of cyclohexanone, and the previously prepared solution was added dropwise at 85 ° C for 4 hours under a nitrogen atmosphere. The reaction solution was stirred with heating for 2 hours, and then left to cool to room temperature. The obtained reaction solution was added dropwise to 1300 g of a mixed solution of heptane/ethyl acetate (9/1 (mass ratio)) to reprecipitate the polymer. The precipitate was filtered, whereby 28.8 g of a resin (P-1) was obtained.

In the following, in the synthesis of the resin (P-1), the monomers to be used are separately changed, and the resin is synthesized in the same manner as the synthesis of the resin (P-1). (P-2) ~ Resin (P-16). The structure, weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) of the synthesized polymer (resin (P-2) to resin (P-16)) are shown below. Further, the composition ratio of each repeating unit of the following polymer structure is represented by a molar ratio.

The acid generator used is shown below.

Hereinafter, the low molecular compound used is shown.

Basic compound

TBAH: tetrabutylammonium hydroxide

TBAB: tetrabutylammonium benzoate

TOA: tris(n-octyl)amine

TPI: 2,4,5-triphenylimidazole

Solvent

S1: PGMEA (b.p.=146°C)

S2: PGME (b.p.=120°C)

S3: cyclohexanone (b.p.=157°C)

S4: γ-butyrolactone

Surfactant

W-1: Megafac R08 (made by Di Ansheng (DIC) Co., Ltd., fluorine and lanthanide)

W-2: Polyoxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., 矽)

W-3: Troysol S-366 (manufactured by Troy Chemical Co., Ltd., fluorine)

W-4: PF6320 (manufactured by OMNOVA, fluorine)

Developer ‧ eluent

G-1: butyl acetate

G-2: 2-heptanone

G-3: anisole

G-4: 4-methyl-2-pentanol

G-5: 1-hexanol

G-6: decane

[Example 1-1 to Example 1-20, Comparative Example 1-1 to Comparative Example 1-4 (EUV exposure (alkali development))]

(1) Preparation and coating of sensitized ray-sensitive or radiation-sensitive resin composition

The resin composition having the composition shown in the following table was subjected to microfiltration using a membrane filter having a pore diameter of 0.05 μm to obtain a sensitized ray-sensitive or radiation-sensitive resin composition (resist composition) (solid content concentration: 1.5) quality%).

The sensitizing ray-sensitive or radiation-sensitive resin composition was applied to a previously treated Hexamethyldisilazane (HMDS) treatment using a spin coater Mark 8 manufactured by Tokyo Electron. On a 6 Å (Si) wafer, it was dried on a hot plate at 100 ° C for 60 seconds to obtain a resist film having a film thickness of 50 nm.

(2) EUV exposure and development

The wafer having the resist film obtained in the above (1) was subjected to an EUV exposure apparatus (Micro Exposure Tool manufactured by Exetech Co., Ltd., and a numerical aperture (NA) of 0.3). , Quadrupole, outer σ (outer sigma) is 0.68, inner σ (inner sigma) is 0.36), and exposure exposure is performed using an exposure mask (line/gap=1/1). After the pattern was exposed, the wafer was heated at 110 ° C for 60 seconds on a hot plate, and then immersed in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds. Then, the wafer was rinsed with water for 30 seconds and dried to obtain a wafer having a resist pattern having a line width of 50 nm and a 1:1 line and a gap pattern.

(3) Evaluation of resist pattern

Using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.), the obtained resist pattern was evaluated for sensitivity and resolution by the following method. The results are shown in the table below.

(3-1) Sensitivity

The irradiation energy at the time of analyzing the 1:1 line having a line width of 50 nm and the gap pattern was taken as the sensitivity (Eop). The smaller the value, the better the performance.

(3-2) Resolution

The minimum line width of the (1:1) line and gap pattern separated under the Eop is taken as the resolution. The smaller the value, the better the performance.

As is apparent from the above Table 1, Examples 1-1 to 1-20 can satisfy both high sensitivity and highness as compared with Comparative Example 1-1 to Comparative Example 1-4 in which the composition of the present invention is not used. Analytical.

Further, in Comparative Example 1-3, since the low molecular compound M-3 as a crosslinking agent was crosslinked with a polar group, even if alkali development was performed, the exposed portion was not removed, and a desired pattern could not be obtained.

[Example 2-1 to Example 2-20, Comparative Example 2-1 to Comparative Example 2-4 (EUV exposure (organic solvent development))]

The composition was changed as shown in the following table, and instead of the alkaline aqueous solution (TMAH; 2.38 mass% aqueous solution of tetramethylammonium hydroxide), the organic developing solution described in the following table was used for development, and the following table was used instead of water. In the same manner as in Example 1-1, the preparation of the sensitizing ray-sensitive or radiation-sensitive resin composition and pattern formation were carried out in the same manner as in Example 1-1. In the following table, in the examples in the column of the eluent, "None" is not eluted.

Evaluation of resist pattern

Using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.), the obtained results were obtained by the same methods as those of Examples 1-1 to 1-20 and Comparative Examples 1-1 to 1-4. The resist pattern evaluates sensitivity and resolution. The results are shown in the table below.

As is apparent from the above Table 2, Examples 2-1 to 2-20 can satisfy both high sensitivity and highness as compared with Comparative Examples 2-1 to 2-4 in which the composition of the present invention is not used. Analytical.

Further, in Comparative Example 2-3, since the low molecular compound M-3 as a crosslinking agent was crosslinked with a polar group, when the organic solvent was developed, the exposed portion was removed, and a desired pattern could not be obtained.

Claims (16)

A pattern forming method comprising: a step of forming a film using a photosensitive ray-sensitive or radiation-sensitive resin composition of the following (i) or (ii); a step of exposing the film; and using an alkali developer a step of removing the exposed portion of the exposed film to form a pattern, (i) a photosensitive ray-sensitive or radiation-sensitive resin composition containing the resin (A1), wherein the resin (A1) contains: a repeating unit in which a group of a group having a polar group is decomposed by an action of an acid, and a repeating unit containing a partial structure having no monovalent iodine atom which is not removed by irradiation with actinic rays or radiation, and the resin (A1) contains a repeating unit represented by the following formula (1'); (ii) a sensitizing ray-sensitive or radiation-sensitive resin composition containing a resin (A2) and a compound (AD) having a monovalent iodine atom, wherein the resin (A2) a repeating unit containing a group having a polar group which is decomposed by the action of an acid, In the formula (1'), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; and R ₁₃ may also bond with Ar _{1 ;} to form a ring, in the case when R ₁₃ is bonded to Ar _1, R ₁₃ represents an alkylene group; X ₁ represents a single bond, alkylene, aromatic ring group, -O -, - S -, - CO -, - COO-, -SO ₂ NH-, -SO ₂ O-, -NR-, a divalent nitrogen-containing non-aromatic heterocyclic group, or a divalent linking group comprising a combination of the groups; R represents a hydrogen atom or Alkyl; Ar ₁ represents an aromatic ring group; RI represents an iodine atom or an organic group containing at least one iodine atom; and n represents an integer of 2 or more. A pattern forming method comprising: a step of forming a film using a photosensitive ray-sensitive or radiation-sensitive resin composition of the following (i) or (ii); a step of exposing the film; and using an organic solvent-containing a developing solution for removing a non-exposed portion of the exposed film to form a pattern, (i) a photosensitive ray-sensitive or radiation-sensitive resin composition containing the resin (A1), wherein the resin (A1) contains: a repeating unit having a group which generates a polar group by decomposition by an action of an acid, and a repeating unit containing a partial structure which is not desorbed by irradiation of actinic rays or radiation and has a monovalent iodine atom, the resin ( A1) a repeating unit represented by the following formula (1'); (ii) a sensitizing ray-sensitive or radiation-sensitive resin composition containing a resin (A2) and a compound (AD) having a monovalent iodine atom, wherein The resin (A2) contains a repeating unit having a group which generates a polar group by decomposition by an action of an acid, In the formula (1'), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; and R ₁₃ may also bond with Ar _{1 ;} to form a ring, in the case when R ₁₃ is bonded to Ar _1, R ₁₃ represents an alkylene group; X ₁ represents a single bond, alkylene, aromatic ring group, -O -, - S -, - CO -, - COO-, -SO ₂ NH-, -SO ₂ O-, -NR-, a divalent nitrogen-containing non-aromatic heterocyclic group, or a divalent linking group comprising a combination of the groups; R represents a hydrogen atom or Alkyl; Ar ₁ represents an aromatic ring group; RI represents an iodine atom or an organic group containing at least one iodine atom; and n represents an integer of 2 or more. The pattern forming method according to claim 1, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition is the sensitized ray-sensitive or radiation-sensitive resin composition (i). The pattern forming method according to claim 2, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition is the sensitized ray-sensitive or radiation-sensitive resin composition (i). The pattern forming method according to claim 1, wherein the content of the resin (A1) is based on the total solid content in the sensitized ray-sensitive or radiation-sensitive resin composition (i) 25 mass% to 99 mass%. The pattern forming method according to claim 2, wherein the total solid content in the photosensitive ray-sensitive or radiation-sensitive resin composition (i) is based The content of the resin (A1) is from 25% by mass to 99% by mass. The pattern forming method according to claim 1, wherein the RI in the formula (1') is an iodine atom. The pattern forming method according to claim 1, wherein X ₁ in the formula (1') is -COO-. The pattern forming method according to any one of claims 1 to 6, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains (B) irradiation by actinic rays or radiation An acid-producing compound. The pattern forming method according to any one of claims 1 to 6, wherein the resin (A1) contains a repeating unit having a group which generates an acid by irradiation with actinic rays or radiation. The pattern forming method according to any one of claims 1 to 6, wherein the exposure is exposure using extreme ultraviolet light. A method of producing an electronic component, comprising the pattern forming method according to any one of claims 1 to 6. An electronic component manufactured by the method of manufacturing an electronic component according to claim 12 of the patent application. A photosensitive ray- or radiation-sensitive resin composition for use in a pattern forming method, and is the following (i) or (ii), wherein the pattern forming method includes: using sensitizing ray or radiation a step of forming a film by a resin composition; a step of exposing the film; and a step of removing an exposed portion of the exposed film using an alkali developing solution to form a pattern, (i) containing a resin (A1) A photosensitive ray-sensitive or radiation-sensitive resin composition, wherein the resin (A1) contains: a repeating unit having a group which generates a polar group by decomposition by an action of an acid, and contains no actinic rays or radiation a repeating unit having a partial structure having a monovalent iodine atom, wherein the resin (A1) contains a repeating unit represented by the following formula (1'); (ii) contains a resin (A2) and has a a sensitizing ray-sensitive or radiation-sensitive resin composition of a compound (AD) having an iodine atom, wherein the resin (A2) contains a repeating unit having a group which generates a polar group by decomposition of an acid, In the formula (1'), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; and R ₁₃ may also bond with Ar _{1 ;} to form a ring, in the case when R ₁₃ is bonded to Ar _1, R ₁₃ represents an alkylene group; X ₁ represents a single bond, alkylene, aromatic ring group, -O -, - S -, - CO -, - COO-, -SO ₂ NH-, -SO ₂ O-, -NR-, a divalent nitrogen-containing non-aromatic heterocyclic group, or a divalent linking group comprising a combination of the groups; R represents a hydrogen atom or An alkyl group; Ar ₁ represents an aromatic ring group; RI represents an iodine atom or an organic group containing at least one iodine atom; and n represents an integer of 2 or more. A photosensitive ray- or radiation-sensitive resin composition for use in a pattern forming method, and is the following (i) or (ii), wherein the pattern forming method includes: using sensitizing ray or radiation a resin composition to form a film; a step of exposing the film; and a step of removing the unexposed portion of the exposed film to form a pattern using a developing solution containing an organic solvent, (i) containing a resin A photosensitive ray-sensitive or radiation-sensitive resin composition of (A1), wherein the resin (A1) contains a repeating unit having a group which generates a polar group by decomposition by an action of an acid, and contains no photochemical a repeating unit having a partial structure of a monovalent iodine atom which is detached by irradiation of radiation or radiation, the resin (A1) containing a repeating unit represented by the following formula (1'); (ii) containing a resin (A2) And a sensitizing ray-sensitive or radiation-sensitive resin composition of a compound (AD) having a monovalent iodine atom, wherein the resin (A2) contains a repeating unit having a group which generates a polar group by decomposition by an action of an acid , In the formula (1'), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; and R ₁₃ may also bond with Ar _{1 ;} to form a ring, in the case when R ₁₃ is bonded to Ar _1, R ₁₃ represents an alkylene group; X ₁ represents a single bond, alkylene, aromatic ring group, -O -, - S -, - CO -, - COO-, -SO ₂ NH-, -SO ₂ O-, -NR-, a divalent nitrogen-containing non-aromatic heterocyclic group, or a divalent linking group comprising a combination of the groups; R represents a hydrogen atom or Alkyl; Ar ₁ represents an aromatic ring group; RI represents an iodine atom or an organic group containing at least one iodine atom; and n represents an integer of 2 or more. A resist film formed of the sensitized ray-sensitive or radiation-sensitive resin composition as described in claim 14 or 15.