JP2010197618A - Active light sensitive or radiation sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

An actinic ray or radiation sensitive material that simultaneously satisfies high sensitivity, high resolution, good pattern shape, and good line edge roughness in an ultrafine region, particularly in electron beam, X-ray or EUV light lithography. An object of the present invention is to provide a conductive resin composition and a pattern forming method using the same.
A repeating unit (A) having an ionic structure site, which decomposes upon irradiation with actinic rays or radiation to generate an acid, at least one phenolic hydroxyl group, and a hydrogen atom of the hydroxyl group. The ionicity of the repeating unit (A) of the resin (P) containing a resin (P) having a repeating unit (B) having a group protected partly or entirely by a group capable of leaving by the action of an acid. An actinic ray-sensitive or radiation-sensitive resin characterized in that the structural site is a structure that generates an acid anion in the side chain of the resin upon irradiation with actinic rays or radiation, and the pKa of the generated acid is 0 or less Composition and pattern formation method using the same.
[Selection figure] None

Description

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other photofabrication processes, and a pattern forming method using the same More particularly, the present invention relates to a resin composition for electron beam, X-ray or EUV light exposure and a pattern forming method using the same.
In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Accordingly, the wavelength of radiation used for exposure tends to be shortened from g-line to i-line, and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light is also being developed.

In particular, electron beam lithography is positioned as a next-generation or next-generation pattern formation technique, and a positive resist with high sensitivity and high resolution is desired. In particular, high sensitivity is an extremely important issue for shortening the wafer processing time. However, in positive resists for electron beams, when trying to increase sensitivity, not only the resolution is lowered, but also the line edge. Roughness deteriorates, and development of a resist that satisfies these characteristics at the same time is strongly desired. Here, the line edge roughness means that when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Say that the edge looks uneven. The unevenness is transferred by an etching process using a resist as a mask, and the electrical characteristics are deteriorated, so that the yield is lowered. Especially 0.2
In the ultrafine region of 5 μm or less, line edge roughness is an extremely important improvement issue. High sensitivity, high resolution, good pattern shape, and good line edge roughness are in a trade-off relationship, and it is very important how to satisfy them simultaneously.

  Similarly, in lithography using X-rays or EUV light, it is important to satisfy high sensitivity, high resolution, good pattern shape, and good line edge roughness at the same time. is required.

  As one method for solving these problems, use of a resin having a photoacid generator (sulfonium group) in a polymer main chain or a side chain has been studied (Patent Documents 1 and 2). However, in the studies in Patent Documents 1 and 2, since the acid itself generated by exposure is a low molecular weight monomer, there is a problem in acid diffusibility in the resist film, and high resolution and good line edge roughness are obtained. It was difficult to achieve. On the other hand, studies have been conducted in which an acid generated by exposure is bound to a polymer (Patent Documents 3 to 7, Non-Patent Document 1), but high sensitivity, high resolution, and good pattern shape in an ultrafine region. At present, good line edge roughness is not satisfied at the same time.

JP-A-2-302758 JP 2006-215526 A JP-A-9-325497 JP-A-10-221852 JP 2006-178317 A International Publication No. 06/121096 Pamphlet US Patent Application Publication No. 2007/0117043

Proc. Of SPIE Vol. 6923, 692312, 2008

  The object of the present invention is to provide high sensitivity, high resolution, good pattern shape, and good line edge roughness in the ultrafine region, particularly in lithography using actinic rays or radiation such as electron beam, X-ray or EUV light. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that satisfies the requirements and a pattern forming method using the same.

(1) a repeating unit (A) having an ionic structure site and decomposing upon irradiation with actinic rays or radiation to generate an acid;
A resin (P) having at least one phenolic hydroxyl group and a repeating unit (B) having a group in which part or all of the hydrogen atoms of the hydroxyl group are protected by a group capable of leaving by the action of an acid. Contains,
The ionic structure site of the repeating unit (A) of the resin (P) has a structure that generates an acid anion in the side chain of the resin upon irradiation with actinic rays or radiation, and the generated acid has a pKa of 0 or less. An actinic ray-sensitive or radiation-sensitive resin composition characterized by the above.

(2) The actinic ray-sensitive or radiation-sensitive resin composition as described in (1) above, wherein the acid anion has a structure represented by the following general formula (X).

In general formula (X),
Rf ₁ represents any of an alkylene group, a cycloalkylene group, an arylene group, and a combination thereof, at least a part of which is substituted with a fluorine atom or a fluoroalkyl group.

(3) The actinic ray-sensitive or radiation-sensitive resin as described in (1) or (2) above, wherein the repeating unit (B) is a repeating unit represented by the following general formula (I): Composition.

Here, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₀₃ represents an alkylene group and may be bonded to Ar ₁ to form a 5-membered or 6-membered ring.
Ar ₁ represents an aromatic ring group.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.

(4) The actinic ray-sensitive or radiation-sensitive resin composition as described in (3) above, wherein Y in the general formula (I) is represented by the following general formula (II).

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group, an alicyclic group which may contain a hetero atom, an aromatic ring group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. .
At least two of Q, M, and L ₁ may combine to form a 5-membered or 6-membered ring.

(5) The activity according to any one of (1) to (4) above, wherein the resin (P) further has a repeating unit (C) represented by the following general formula (VI): A light-sensitive or radiation-sensitive resin composition.

Here, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₀₃ represents an alkylene group and may be bonded to Ar ₁ to form a 5-membered or 6-membered ring.
Ar ₁ represents an aromatic ring group.
n represents an integer of 1 to 4.

(6) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5) above, wherein the resin (P) has a weight average molecular weight in the range of 1000 to 100,000. object.

(7) The resin (P) has a repeating unit (A) of 0.5 to 80 mol%, a repeating unit (B) of 3 to 90 mol%, and a repeating unit (C) of 3 to 90 mol%. The actinic ray-sensitive or radiation-sensitive resin composition as described in (5) or (6) above.

(8) The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of (1) to (7) above, further comprising a basic compound.
(9) The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of (1) to (8) above, which is for exposure with an electron beam, X-ray or EUV light.
(10) A pattern comprising the steps of forming a film, exposing and developing using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (9) above. Forming method.

  According to the present invention, actinic ray sensitivity that satisfies simultaneously high sensitivity, high resolution, good pattern shape, and good line edge roughness in an ultrafine region, particularly in electron beam, X-ray or EUV light lithography, or A radiation-sensitive resin composition and a pattern forming method using the same can be provided. The actinic ray-sensitive or radiation-sensitive resin composition described in the above (1) to (8) is a so-called positive type, and can be suitably used as a positive type resist composition.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “exposure” in the present specification is represented not only by exposure to deep ultraviolet rays, X-rays, EUV light and the like, but also by particle beams such as electron beams and ion beams, unless otherwise specified, such as mercury lamps and excimer lasers. Drawing is also included in the exposure.

<Resin (P)>
The resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition has an ionic structure site, and is a repeating unit (A) that decomposes upon irradiation with actinic rays or radiation to generate an acid, and at least A repeating unit (B) having one phenolic hydroxyl group and a group in which part or all of the hydrogen atoms of the hydroxyl group are protected by a group capable of leaving by the action of an acid. The ionic structure portion of the resin is a structure in which an acid anion is generated in the side chain of the resin (P) by irradiation with actinic rays or radiation, and the generated acid has a pKa of 0 or less. is there.

(1) Repeating unit (A)
The repeating unit (A) is a repeating unit that has an ionic structure site and decomposes upon irradiation with actinic rays or radiation to generate an acid, and the ionic structure site is irradiated with actinic rays or radiation. Any structure can be used as long as it has a structure in which an acid anion is generated in the side chain of the resin and the pKa of the generated acid is 0 or less.
Here, the pKa of the generated acid represents the pKa calculated from “ACD / pKa DB V8.0 (manufactured by Advanced Chemistry Development, Inc.)”.
In “ACD / pKa DB V8.0 (manufactured by Advanced Chemistry Development, Inc.)”, a database of Hammett's formula, substituent constants, and known literature values (a chemical structure of 16000 and an actual measurement value of 31,000 or more) for an arbitrary organic structure. Can be used to calculate the acid dissociation constant (pKa) in aqueous solution (25 ° C., ionic strength 0).
When the repeating unit (A) is irradiated with actinic rays or radiation, a repeating unit (A ′) having an acid anion is generated. By calculating the pKa of the monomer necessary for constituting this repeating unit (A ′) by “ACD / pKa DB V8.0 (manufactured by Advanced Chemistry Development, Inc.)”, pKa can be calculated. it can. Although it does not specifically limit, For example, pKa in the following repeating unit (A) can be calculated as the following table | surface.

  As pKa, -0.5 or less is more preferable, and -1.0 or less is particularly preferable. The lower limit of pKa is preferably -5.0.

  The repeating unit (A) is preferably a repeating unit in which the generated acid anion has a structure represented by the following general formula (X).

In general formula (X),
Rf ₁ represents any of an alkylene group, a cycloalkylene group, an arylene group, and a combination thereof, at least a part of which is substituted with a fluorine atom or a fluoroalkyl group.
That is, the alkylene group, cycloalkylene group, arylene group, and group obtained by combining these as Rf ₁ have at least one of a fluorine atom and a fluoroalkyl group as a substituent.

Rf ₁ is more preferably an alkylene group, an arylene group, or a combination thereof, in which at least a part is substituted with a fluorine atom or a fluoroalkyl group (more preferably a perfluoroalkyl group), and at least a part is a fluorine atom. An alkylene group and an arylene group substituted with are particularly preferable.
In the group represented by Rf ₁ , the position where the fluorine atom is substituted is preferably close to the sulfonate anion, and the fluorine atom is bonded to the carbon atom adjacent to the sulfonate anion (α position). More preferred.

The alkylene group in which at least a part of Rf ₁ is substituted with a fluorine atom or a fluoroalkyl group is not particularly limited, but is a linear or branched group having 1 to 10 carbon atoms in which at least a part is substituted with a fluorine atom. An alkylene group is preferred.

In the group represented by the general formula (X), the group in which Rf ₁ is an alkylene group at least partially substituted with a fluorine atom or a fluoroalkyl group is represented by the following general formula (X-1). Are particularly preferred.

In general formula (X-1),
Rf ₂ and Rf ₃ each independently represents a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
Rf ₄ represents a single bond or a fluorine atom in an optionally substituted alkylene group having 1 to 5 carbon atoms.
However, Rf ₂ and Rf ₃ do not represent hydrogen atoms at the same time.

The cycloalkylene group in which at least a part of Rf ₁ is substituted with a fluorine atom or a fluoroalkyl group is not particularly limited, but a cycloalkylene group having 3 to 10 carbon atoms in which at least a part is substituted with a fluorine atom is preferable.

The arylene group in which at least a part of Rf ₁ is substituted with a fluorine atom or a fluoroalkyl group is not particularly limited, but an arylene group having 6 to 10 carbon atoms in which at least a part is substituted with a fluorine atom or a fluoroalkyl group ( For example, a phenylene group or a naphthylene group) is preferable.

Examples of the combination of an alkylene group, a cycloalkylene group, and an arylene group in which at least a part of Rf ₁ is substituted with a fluorine atom or a fluoroalkyl group include, for example, a part of which is substituted with a fluorine atom or a fluoroalkyl group A combination of a linear or branched alkylene group having 1 to 10 carbon atoms and a cycloalkylene group having 3 to 10 carbon atoms, at least a part of which is substituted with a fluorine atom or a fluoroalkyl group, part Is a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or a fluoroalkyl group, and 6 to 10 carbon atoms having at least a part substituted with a fluorine atom or a fluoroalkyl group. A number of carbon atoms in which at least a part of the group is a fluorine atom or a fluoroalkyl group A group consisting of a linear or branched alkylene group having 10 to 10 carbon atoms and a cycloalkylene group having 3 to 10 carbon atoms, a straight chain having 1 to 10 carbon atoms in which at least a part is substituted with a fluorine atom or a fluoroalkyl group A group in which a chain or branched alkylene group and an arylene group having 6 to 10 carbon atoms are combined is preferable.

As the fluoroalkyl group in the case of having a group substituents as Rf _1, preferably perfluoroalkyl group, more preferably a trifluoromethyl group.

  Specific examples of the structure represented by the general formula (X) are shown below, but the present invention is not limited thereto.

  As said repeating unit (A), the repeating unit represented by either of the following general formula (III)-(V) is preferable, for example.

Here, R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₆ represents a cyano group, a carboxyl group, —CO—OR ₂₅ or —CO—N (R ₂₆ ) (R ₂₇ ). R ₂₆ and R ₂₇ may combine to form a ring with the nitrogen atom.
X _{1 to} X ₃ are each independently a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R ₃₃ ) —, or a combination thereof. Represents a divalent linking group.
R ₂₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
R ₂₆ , R ₂₇ and R ₃₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
A represents an ionic structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion represented by the general formula (X) in the resin side chain.

In the general formulas (III) to (V), the alkyl groups represented by R _{04 to} R ₀₅ and R _{07 to} R ₀₉ are preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group that may have a substituent. Group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group and the like, and an alkyl group having 20 or less carbon atoms, and more preferably an alkyl group having 8 or less carbon atoms. .
Examples of the cycloalkyl group include cycloalkyl groups that may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.
Examples of the alkyl group contained in the alkoxycarbonyl group include R _{04 to} R ₀₅ , R ₀₇ to
The same alkyl group as R ₀₉ is preferable.

Preferred alkyl groups and cycloalkyl groups for R _{25 to} R ₂₇ and R ₃₃ are the same as the above-mentioned preferred alkyl groups and cycloalkyl groups for R _{04 to} R ₀₅ and R _{07 to} R ₀₉ .
Preferred examples of the alkenyl group include those having 2 to 6 carbon atoms, such as a vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, and cyclohexenyl group which may have a substituent. It is done.
As the aryl group, a monocyclic or polycyclic aromatic group having 6 to 14 carbon atoms which may have a substituent is preferable. Specifically, a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, A naphthyl group etc. are mentioned. In addition, aryl groups may be bonded to form a multicycle.
Examples of the aralkyl group include those having 7 to 15 carbon atoms which may have a substituent such as a benzyl group, a phenethyl group, or a cumyl group.
The ring formed by combining R ₂₆ and R ₂₇ together with the nitrogen atom is preferably a ring that forms a 5- to 8-membered ring. Specific examples include pyrrolidine, piperidine, and piperazine.

The arylene group of X _{1 to} X ₃ is preferably an arylene group having 6 to 14 carbon atoms which may have a substituent, and specific examples thereof include a phenylene group, a tolylene group and a naphthylene group.
The alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.
Preferred examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.

Preferred substituents for each group in the general formulas (III) to (V) include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, R ₀₄ to The alkyl groups, methoxy groups, ethoxy groups mentioned in R ₀₉ , R _{25 to} R ₂₇ , R ₃₃ ;
Alkoxy groups such as hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, acyl groups such as formyl group, acetyl group, benzoyl group, acetoxy group, butyryloxy group, etc. These include an acyloxy group and a carboxy group, and the substituent preferably has 8 or less carbon atoms.

  A represents an ionic structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion represented by the general formula (X) in the resin side chain.

  A is preferably an ionic structural site containing an onium salt, and more preferably an ionic structural site containing a sulfonium salt or an iodonium salt. More specifically, A is preferably a group represented by the following general formula (ZI) or (ZII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Rf ₁ has the same meaning as Rf ₁ in formula (X).

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the groups represented by (ZI-1), (ZI-2) and (ZI-3) described later. .

  More preferable examples of the group represented by (ZI) include a (ZI-1) group, a (ZI-2) group, and a (ZI-3) group described below.

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

All of R ₂₀₁ to R ₂₀₃ may be an aryl group or a part of R ₂₀₁ to R ₂₀₃ is an aryl group and the remainder may be an alkyl group or a cycloalkyl group.

  For example, groups corresponding to triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, aryldicycloalkylsulfonium can be exemplified.

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

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

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the (ZI-2) group will be described.
The (ZI-2) group is a group in which R _{201 to} R ₂₀₃ in the general formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R _203, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.
The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

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

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

In general formula (ZI-3),
R _1c to R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R _x and R _y independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom and a sulfur atom. , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
Rf ₁ has the same meaning as Rf ₁ in formula (X).

The alkyl group as R _1c to R _7c may be linear or branched may be any of, for example, alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 linear or branched alkyl group having a carbon number ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 8 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

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

Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c , such as a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxy group. A carbonylmethyl group is more preferred.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .
Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as in R _{1c to} R _5c .

R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

In the general formula (ZII), R ₂₀₄ ~R ₂₀₅ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Aryl group, alkyl group of R ₂₀₄ to R _205, specific examples of the cycloalkyl group include aryl groups mentioned in the previous (ZI-1) group, an alkyl group, the same cycloalkyl group .

Aryl group, alkyl group of R ₂₀₄ to R _205, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _205, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

Rf ₁ has the same meaning as Rf ₁ in formula (X).

  Although the preferable specific example of A is given below, this invention is not specifically limited to these.

As the repeating unit represented by any one of the general formulas (III) to (V) effectively used in the present invention, more preferably, the following general formulas (III-1) to (III-6), What is represented by either (IV-1)-(IV-4) and general formula (V-1)-(V-2) can be mentioned.

In the general formula, Ar _1a represents an arylene group which may have a substituent, similar to the arylene groups represented by X _{1 to} X ₃ .
Ar _{2 a to} Ar _{4 a} may have a substituent similar to the aryl groups represented by R _{201 to} R ₂₀₃ and R _{204 to} R ₂₀₅ in the general formulas (ZI) and (ZII). Represents an aryl group.
R ₀₁ represents a hydrogen atom, a methyl group, a chloromethyl group, a trifluoromethyl group or a cyano group.
R ₀₂ and R ₀₂₁ are the same as those represented by X _{1 to} X ₃ , such as a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, CO—, —N (R ₃₃ )-Or a divalent linking group in which a plurality of these are combined.

R ₀₃ and R ₀₁₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Examples of the alkyl group and cycloalkyl group include the same alkyl groups and cycloalkyl groups as R _{01 to} R ₀₃ in the general formula (I) described later. As an aryl group and an aralkyl group, the same thing as the aryl group and aralkyl group as L < ₁ > -L < ₂ > in postscript general formula (II) can be mentioned.

Rf ₁ has the same meaning as Rf ₁ in formula (X).

The content of the repeating unit (A) in the resin of the present invention is preferably in the range of 0.5 to 80 mol%, and preferably in the range of 1 to 60 mol% with respect to all the repeating units. Is more preferable, and it is especially preferable to contain in 3-40 mol%.
A method for synthesizing the monomer corresponding to the repeating unit (A) is not particularly limited. For example, the acid anion having a polymerizable unsaturated bond corresponding to the repeating unit and a known onium salt halide are exchanged. A method is mentioned.
More specifically, a metal ion salt (for example, sodium ion, potassium ion, etc.) or an ammonium salt (ammonium, triethylammonium salt, etc.) of an acid having a polymerizable unsaturated bond corresponding to the repeating unit, and a halogen ion ( An onium salt having a chloride ion, bromide ion, iodide ion, etc.) is stirred in the presence of water or methanol to carry out an anion exchange reaction, such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone, tetrahydroxyfuran, etc. By performing a liquid separation / washing operation with an organic solvent and water, a monomer corresponding to the desired repeating unit (A) can be synthesized.
After anion exchange reaction by stirring in the presence of an organic solvent that can be separated from water, such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone, and tetrahydroxyfuran, and water separation, washing with water It can also be synthesized by operating.

  Specific examples of the repeating unit represented by any one of the general formula (III) to the general formula (V) are shown below as preferred specific examples of the repeating unit (A), but the present invention is not limited thereto. Absent.

(2) Repeating unit (B)
The repeating unit (B) of the resin (P) has at least one phenolic hydroxyl group, and has a group in which part or all of the hydrogen atoms of the hydroxyl group are protected by a group capable of leaving by the action of an acid. It is a repeating unit.
The repeating unit (B) has at least one phenolic hydroxyl group, and a repeating unit having a group protected by a group in which some or all of the hydrogen atoms of the hydroxyl group are eliminated by the action of an acid. Any of them can be used.

  As the repeating unit (B), for example, a repeating structural unit represented by the following general formula (I) is preferable.

Here, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₀₃ represents an alkylene group and may be bonded to Ar ₁ to form a 5-membered or 6-membered ring.
Ar ₁ represents an aromatic ring group.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4, preferably 1 to 2, and more preferably 1.

As the alkyl group of R _{01 to} R ₀₃ in the general formula (I), a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, which may preferably have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, and more preferable examples include alkyl groups having 8 or less carbon atoms.
The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R _{01 to} R ₀₃ .
Examples of the cycloalkyl group include cycloalkyl groups that may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.
When R ₀₃ represents an alkylene group, the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group.

The aromatic ring group of Ar ₁ preferably has 6 to 14 carbon atoms which may have a substituent, and specific examples thereof include a benzene ring, a toluene ring, a naphthalene ring and the like.

n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of n represents a group capable of leaving by the action of an acid.
Examples of the group Y leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ). ), -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ) -C (= O) -O-C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —CH (R ₃₆ ) (Ar) and the like can be mentioned.

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
Ar represents an aryl group.
The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, octyl group and the like.
The cycloalkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group. Group, androstanyl group and the like. A part of 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 a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group of 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 naphthylmethyl group.
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 combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkane structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. As the polycyclic type, a cycloalkane structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. A part of carbon atoms in the cycloalkane structure may be substituted with a hetero atom such as an oxygen atom.
Each of the above groups as R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ , R _03, Ar and Ar ₁ may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, Aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc. And the substituent has preferably 8 or less carbon atoms.

  The group Y that is eliminated by the action of an acid is more preferably a structure represented by the following general formula (II).

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group, an alicyclic group which may contain a hetero atom, an aromatic ring group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. .
At least two of Q, M, and L ₁ may combine to form a 5-membered or 6-membered ring.

The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group. An octyl group can be preferably mentioned.
The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specifically, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group can be preferably exemplified.
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 anthryl group.
The aralkyl group as L ₁ and L ₂ has, for example, 6 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.), cycloalkylene group (for example, cyclopentylene group, cyclohexylene group). Group), alkenylene group (for example, ethylene group, propenylene group, butenylene group, etc.), arylene group (for example, phenylene group, tolylene group, naphthylene group, etc.), -S-, -O-, -CO-, -SO _2- , -N (R ₀ )-, and a divalent linking group in which a plurality of these are combined. R ₀ represents a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group). Octyl group, etc.).
The alkyl group and cycloalkyl group as Q are the same as the above groups as L ₁ and L ₂ .
As the alicyclic group and the aromatic ring group in the alicyclic group which may contain a hetero atom as Q and the aromatic ring group which may contain a hetero atom, the cycloalkyl as L ₁ and L ₂ described above is used. Group, an aryl group, etc. are mentioned, Preferably it is C3-C15.
Examples of the alicyclic group containing a hetero atom and the aromatic ring group containing a hetero atom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. And groups having a heterocyclic structure such as pyrrolidone, but are not limited to these as long as the structure is generally called a heterocyclic ring (a ring formed of carbon and a heteroatom, or a ring formed of a heteroatom). .

As a 5-membered or 6-membered ring that may be formed by combining at least two of Q, M, and L ₁ , at least two of Q, M, and L ₁ are combined to form, for example, a propylene group and a butylene group In this case, a 5-membered or 6-membered ring containing an oxygen atom is formed.
Each group represented by L ₁ , L ₂ , M, and Q in the general formula (II) may have a substituent. For example, R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ , _{Examples of the} substituent that may be possessed by R _03, Ar and Ar ₁ are mentioned, and the substituent preferably has 8 or less carbon atoms.

  The group represented by -MQ is preferably a group composed of 1 to 30 carbon atoms, more preferably a group composed of 5 to 20 carbon atoms.

  Specific examples of the repeating unit represented by formula (I) are shown below as preferred specific examples of the repeating unit (B), but the present invention is not limited thereto.

The content of the repeating unit (B) in the resin of the present invention is preferably 3 to 90 mol%, more preferably 5 to 80 mol%, based on all repeating units. Preferably, it is contained in the range of 7 to 70 mol%.
The ratio of the repeating unit (A) to the repeating unit (B) in the resin (number of moles of A / number of moles of B) is preferably 0.04 to 1.0, more preferably 0.05 to 0.9. 0.06-0.8 is particularly preferable.

(3) Repeating unit (C)
The resin in the present invention preferably further has a repeating unit (C) represented by the following general formula (VI).

Here, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₀₃ represents an alkylene group and may be bonded to Ar ₁ to form a 5-membered or 6-membered ring.
Ar ₁ represents an aromatic ring group.
n represents an integer of 1 to 4.

In the general formula _{(VI), R 01, R} 02, R 03, and specific examples of Ar ₁ are in the general formula _{(I), R 01, R} 02, R 03, and similarly to the Ar ₁ Can be mentioned.

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

  The content of the repeating unit (C) in the resin of the present invention is preferably 3 to 90 mol%, more preferably 5 to 80 mol%, based on all repeating units. Preferably, it is contained in the range of 7 to 70 mol%.

(4) Form of Resin (P) of the Present Invention, Polymerization Method, Molecular Weight, etc. The form of the resin (P) may be any of random type, block type, comb type, and star type.
The resin (P) according to the present invention having the above repeating units (A) and (B), or the resin (P) according to the present invention having the repeating units (A), (B) and (C), for example, It can be synthesized by radical, cationic or anionic polymerization of unsaturated monomers corresponding to each structure. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.

  The resin according to the present invention preferably has 0.5 to 80 mol% of the repeating unit (A), 3 to 90 mol% of the repeating unit (B), and 3 to 90 mol% of the repeating unit (C).

The molecular weight of the resin (P) according to the present invention is not particularly limited, but the weight average molecular weight is 100.
It is preferably in the range of 0 to 100,000, more preferably in the range of 1500 to 70000, and particularly preferably in the range of 2000 to 50000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).
The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50.

Further, for the purpose of improving the performance of the resin according to the present invention, it may further have repeating units derived from other polymerizable monomers as long as the dry etching resistance is not significantly impaired.
The content of repeating units derived from other polymerizable monomers in the resin is generally 50 mol% or less, preferably 30 mol% or less, based on all repeating units. Other polymerizable monomers that can be used include those shown below. For example, it is a compound having one addition polymerizable unsaturated bond selected from (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters and the like. .
Specifically, (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Amyl acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid-t-octyl, (meth) acrylic acid 2-chloroethyl, (meth) acrylic acid 2 -Hydroxyethyl, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate and the like.
(Meth) acrylamides include, for example, (meth) acrylamide, N-alkyl (meth) acrylamide, (the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl Group, t-butyl group, heptyl group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-aryl (meth) acrylamide (as aryl groups, for example, phenyl group, tolyl group , Nitrophenyl group, naphthyl group, cyanophenyl group, hydroxyphenyl group, carboxyphenyl group, etc.), N, N-dialkyl (meth) acrylamide (the alkyl group has 1 to 10 carbon atoms, for example, , Methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Hexyl group, etc.), N, N-aryl (meth) acrylamide (aryl groups include, for example, phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide. N-2-acetamidoethyl-N-acetylacrylamide and the like.

Examples of allyl compounds include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.) Examples include oxyethanol.
Examples of vinyl ethers include alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2- Ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc., vinyl aryl ethers (eg vinyl phenyl ether, vinyl tolyl ether, vinyl chloride) Phenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether) and the like.
Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, Examples thereof include vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.
Examples of styrenes include styrene and alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene). , Trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg, methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.), alkylcarbonyloxy styrene (eg, 4-acetoxy styrene, 4-cyclohexylcarbonyloxystyrene), arylcarbonyloxystyrene (for example, 4-phenylcarbonyloxystyrene) ), Halogen styrene (for example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro) Rumethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), cyanostyrene, carboxystyrene and the like.
Examples of the crotonic acid esters include alkyl crotonic acid (for example, butyl crotonic acid, hexyl crotonic acid, glycerin monocrotonate, etc.).
Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
Examples of the dialkyl esters of maleic acid or fumaric acid include dimethyl maleate and dibutyl fumarate.
In addition, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilonitrile, and the like can be given. In general, any addition-polymerizable unsaturated compound copolymerizable with the repeating unit according to the present invention can be used without any particular limitation.

  Resin (P) of this invention can be used individually by 1 type or in combination of 2 or more types. The content of the resin (P) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, 70 ˜100 mass% is particularly preferred.

  Preferred specific examples of the resin (P) are, for example, one or more repeating units selected from the specific examples of the general formulas (III) to (IV) / selected from the specific examples of the general formula (I). Resin having one or more kinds of repeating units, one or more kinds of repeating units selected from the specific examples of the general formulas (III) to (IV) / one or more kinds selected from the specific examples of the general formula (I) The resin having one or more repeating units selected from the specific examples of the repeating unit / general formula (VI) is not limited thereto.

<Other ingredients>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention includes a basic compound, a resin that decomposes by the action of an acid and increases the dissolution rate with respect to alkaline water solubility, if necessary, a conventional photoacid Generating agents, organic solvents, surfactants, acid-decomposable dissolution inhibiting compounds, dyes, plasticizers, photosensitizers, dissolution-promoting compounds for developers, and compounds having proton acceptor functional groups Can do.

<Basic compound>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a basic compound in order to reduce the change in performance over time from exposure to heating, or to control the diffusibility of acid generated by exposure in the film. May be.

  Preferable basic compounds include basic compounds having structures represented by the following general formulas (A) to (E).

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group (preferably 6 to 20), and R ²⁵⁰ and R ²⁵¹ may be bonded to each other to form a ring.
These may have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to 1 carbon atoms. A 20 hydroxyalkyl group or a C 3-20 hydroxycycloalkyl group is preferred.
These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represents an alkyl group (preferably having 1 to 6 carbon atoms) or a cycloalkyl group (preferably having 3 to 6 carbon atoms).

  Preferable compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, and may have a substituent. Further preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure (particularly preferably tetraalkylammonium hydroxide), onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, hydroxyl group and / or ether. Examples thereof include alkylamine derivatives having a bond, aniline derivatives having a hydroxyl group and / or an ether bond.

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

  Further, at least one nitrogen-containing compound selected from an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group can be exemplified. . These compounds are preferably amine compounds in which at least one alkyl group is bonded to a nitrogen atom. Furthermore, it is preferable that the alkyl chain has an oxygen atom and an oxyalkylene group is formed. Preferable examples of these compounds include, but are not limited to, compounds (C1-1) to (C3-3) exemplified in [0066] of US2007 / 0224539A.

Moreover, you may use a photosensitive basic compound as a basic compound. The photosensitive base compound is not particularly limited. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995)
Etc. can be used.

  The molecular weight of the basic compound is preferably 250 to 2000, and more preferably 400 to 1000.

These basic compounds are used alone or in combination of two or more.
The content of the basic compound is preferably 0 to 8.0 mass%, more preferably 0 to 5.0 mass%, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Especially preferably, it is 0-4.0 mass%. The basic compound is not an essential component in the present invention, but is usually used in an amount of 0.01% by mass or more in order to obtain the effect of adding the basic compound.

<Resin that is decomposed by the action of an acid to increase the dissolution rate with respect to alkaline water solubility>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain, in addition to the resin (P), a resin that decomposes by the action of an acid and increases the dissolution rate with respect to alkali water solubility.

  Resins that decompose due to the action of an acid and increase the dissolution rate in an alkaline aqueous solution (hereinafter also referred to as “acid-decomposable resins”) are not included in the main chain or side chain of the resin, or both of the main chain and side chain. It is a resin having a group (acid-decomposable group) that decomposes by the action of and produces an alkali-soluble group. Among these, a resin having an acid-decomposable group in the side chain is more preferable.

The acid-decomposable resin is a precursor of a group that can be decomposed with an acid into an alkali-soluble resin as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. It can be obtained by copolymerizing an alkali-soluble resin monomer having a group that can be reacted with the body or decomposable with an acid with various monomers.
As the acid-decomposable group, for example, in a resin having an alkali-soluble group such as —COOH group and —OH group, a group in which the hydrogen atom of the alkali-soluble group shown on the left is substituted with a group capable of leaving by the action of an acid is preferable.
Specifically, the acid-decomposable group is preferably the same group as the acid-decomposable group described in the above-described resin of the present invention (for example, the acid-decomposable group described as the repeating unit (B) in the resin (P)). As an example.

  The resin having an alkali-soluble group is not particularly limited. For example, poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene) and copolymers thereof, hydrogenated poly (Hydroxystyrene), poly (hydroxystyrene) s having a substituent represented by the following structure, and resins having a phenolic hydroxyl group, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, hydrogen An alkali-soluble resin having a hydroxystyrene structural unit such as a modified novolak resin, and an alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid or norbornenecarboxylic acid.

  The alkali dissolution rate of these alkali-soluble resins is preferably at least 170 kg / second as measured with 2.38 mass% tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 330 Å / second or more.

  The alkali-soluble resin monomer is not particularly limited. For example, alkylcarbonyloxystyrene (for example, t-butoxycarbonyloxystyrene), alkoxystyrene (for example, 1-alkoxyethoxystyrene, t-butoxystyrene), (meta ) Acrylic acid tertiary alkyl ester (for example, t-butyl (meth) acrylate, 2-alkyl-2-adamantyl (meth) acrylate, dialkyl (1-adamantyl) methyl (meth) acrylate, etc.)) and the like.

  The content ratio of the group capable of decomposing with an acid is the number of repeating units (B) having a group decomposable with an acid in the resin and the number of repeating units having an alkali-soluble group not protected with a group capable of leaving with an acid. With (S), it is represented by B / (B + S). The content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

The acid-decomposable resin is not particularly limited, but preferably has a repeating unit having an aromatic group, and is an acid-decomposable resin having hydroxystyrene as a repeating unit (for example, poly (hydroxystyrene / acid-decomposable group). (Hydroxystyrene) and poly (hydroxystyrene / (meth) acrylic acid protected with an acid-decomposable group)) are more preferred.

  As the acid-decomposable resin, a resin having a repeating unit represented by the following general formula (VI) and a repeating unit represented by the general formula (I) is particularly preferable.

  The general formula (VI) is the same as the general formula (VI), and the general formula (I) is the same as the general formula (I).

The acid-decomposable resin may have a repeating unit derived from another polymerizable monomer.
The content of repeating units derived from other polymerizable monomers in the resin is generally 50 mol% or less, preferably 30 mol% or less, based on all repeating units. Examples of the repeating unit derived from another copolymerizable monomer that can be used include the same repeating unit as the repeating unit derived from the other polymerizable monomer.

  The content of the repeating unit having an alkali-soluble group such as a hydroxyl group, a carboxy group, or a sulfonic acid group is preferably 1 to 99 mol%, more preferably 3 to 95 mol% in all repeating units constituting the acid-decomposable resin. Especially preferably, it is 5-90 mol%.

  The content of the repeating unit having an acid-decomposable group is preferably from 3 to 95 mol%, more preferably from 5 to 90 mol%, particularly preferably from 10 to 85 mol% in all repeating units constituting the acid-decomposable resin. It is.

The weight average molecular weight of the acid-decomposable resin is preferably 50,000 or less, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000 as a polystyrene conversion value by the GPC method.
The dispersity (Mw / Mn) of the acid-decomposable resin is preferably 1.0 to 3.0, more preferably 1.05 to 2.0, and still more preferably 1.1 to 1.7.

  Two or more acid-decomposable resins may be used in combination.

  Although the preferable specific example of an acid-decomposable resin is shown below, it is not limited to these.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the compounding amount in the composition of the acid-decomposable resin excluding the resin (P) is preferably 0 to 70% by mass in the total solid content of the composition, More preferably, it is 0-50 mass%, More preferably, it is 0-30 mass%. The acid-decomposable resin excluding the resin (P) is not an essential component in the present invention, but is usually used at 0.01% by mass or more in order to obtain the effect of addition.

<Acid generator>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (P) having a photoacid-generating structure. In addition to the resin (P), an acid is irradiated by irradiation with actinic rays or radiation. It may contain a low molecular compound that is generated (hereinafter also referred to as “acid generator”).
Examples of such an acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecoloring agent for dyes, a photochromic agent, or an actinic ray or radiation used for a micro resist, etc. A known compound that generates an acid by irradiation and a mixture thereof can be appropriately selected and used.

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

  Among the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, compounds represented by the following general formulas (ZI ′), (ZII ′), and (ZIII ′) can be exemplified.

In general formulas (ZI ′) and (ZII ′),
R ₂₀₁ to R ₂₀₅ have the same meanings as R ₂₀₁ to R ₂₀₅ in formula (ZI) and (ZII).
X ⁻ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{— and the} like. Preferably, it is an organic anion containing a carbon atom.

  More preferable organic anions include organic anions represented by the following general formulas (AN1) to (AN4).

In the general formulas (AN1) and (AN2), Rc ₁ represents an organic group.

Examples of the organic group in Rc ₁ include those having 1 to 30 carbon atoms, and preferably an alkyl group, an aryl group, or a plurality thereof, which may be substituted, is a single bond, —O—, —CO ₂ —, — _{S -, - SO 3 -,} - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as.
Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with the bonded alkyl group or aryl group.
The organic group of Rc ₁ is more preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. When Rc ₁ has 5 or more carbon atoms, it is preferable that at least one carbon atom does not have all the hydrogen atoms replaced by fluorine atoms, but a part of the hydrogen atoms remains. It is more preferable that the number of is greater than that of fluorine atoms. By not having a perfluoroalkyl group having 5 or more carbon atoms, ecotoxicity is reduced.
The most preferred embodiment of Rc ₁ is a group represented by the following general formula.

In the above general formula,
Rc ₆ is substituted with a perfluoroalkylene group having 4 or less carbon atoms, more preferably 2 to 4 carbon atoms, still more preferably 2 to 3 carbon atoms, or 1 to 4 fluorine atoms and / or 1 to 3 fluoroalkyl groups. Represents a phenylene group.
Ax represents a linking group (preferably a single bond, —O—, —CO ₂ —, —S—, —SO ₃ —, —SO ₂ N (Rd ₁ ) —). Rd ₁ represents a hydrogen atom or an alkyl group, and may combine with Rc ₇ to form a ring structure.
Rc ₇ represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group which may be substituted, a monocyclic or polycyclic cycloalkyl group or an aryl group. The optionally substituted alkyl group, cycloalkyl group and aryl group preferably do not contain a fluorine atom as a substituent.

In the general formulas (AN3) and (AN4),
Rc ₃ , Rc ₄ and Rc ₅ represent an organic group.

In the general formulas (AN3) and (AN4), the organic groups represented by Rc ₃ , Rc ₄ , and Rc ₅ are preferably the same as the preferred organic groups in Rc ₁ .
Rc ₃ and Rc ₄ may be bonded to form a ring.
Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group and an arylene group. Preferably, it is a C2-C4 perfluoroalkylene group. Rc ₃ and Rc ₄ are preferably bonded to form a ring, so that the acidity of the acid generated by light irradiation is increased and the sensitivity is improved, which is preferable.

In addition, the compound which has two or more structures represented by general formula (Z1 ') may be sufficient. For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (ZI ′) is bonded to at least one of R _{201 to} R ₂₀₃ of another compound represented by the general formula (ZI ′). It may be a compound having a structure.

In the general formula (ZIII ′),
R _{206 to} R ₂₀₇ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
The aryl group of R _{206 to} R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
The alkyl group as R _{206 to} R ₂₀₇ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group). Butyl group, pentyl group).
The cycloalkyl group as R _{206 to} R ₂₀₇ preferably includes a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
Examples of the substituent that R _{206 to} R ₂₀₇ may have include an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group (for example, 6 to 6 carbon atoms). 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZIV ′), (ZV ′), and (ZVI ′) can be further exemplified.

In general formulas (ZIV ′) to (ZVI ′),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R _<208> represents an alkyl group, a cycloalkyl group, or an aryl group each independently.
R ₂₀₉ and R ₂₁₀ represent an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group. R ₂₀₉ is preferably an aryl group. R ₂₁₀ is preferably an electron withdrawing group, more preferably a cyano group or a fluoroalkyl group.
A represents an alkylene group, an alkenylene group or an arylene group.
These groups may have a substituent, and examples of the substituent include the same substituents that R _{204 to} R ₂₀₇ may have.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, more preferred are the compounds represented by the general formulas (ZI ′), (ZIII ′), (ZVI ′), and even more preferred are the general formulas It is a compound represented by (ZI-1 ′), (ZIII ′), (ZVI ′).

  Among the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, examples of particularly preferable compounds are listed below.

  Moreover, the compound represented by the following general formula (A1) can also be mentioned as a preferable example of an acid generator.

In general formula (A1),
R ^{1a to} R ^13a each independently represents a hydrogen atom or a substituent, and at least one of R ^{1a to} R ^13a is a substituent containing an alcoholic hydroxyl group.
Za is a single bond or a divalent linking group.
X ⁻ represents a counter anion.

  The alcoholic hydroxyl group in the present invention represents a hydroxyl group bonded to a carbon atom of an alkyl group.

When R < ^1a > -R <^13a> is a substituent containing an alcoholic hydroxyl group, R < ^1a > -R <^13a> is represented by -WY. However, Y is an alkyl group substituted with a hydroxyl group, and W is a single bond or a divalent linking group.

The alkyl group of Y is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group Preferably ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group, more preferably ethyl group, propyl group and isopropyl group. Y particularly preferably contains a —CH ₂ CH ₂ OH structure.

  The divalent linking group represented by W is not particularly limited, and examples thereof include an alkoxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an acylamino group, an aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxy Examples thereof include a divalent group in which an arbitrary hydrogen atom in a monovalent group such as a carbonyl group, an alkoxycarbonyl group, or a carbamoyl group is replaced with a single bond.

  W is preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, an alkoxycarbonyl group, and any hydrogen atom in the carbamoyl group replaced with a single bond. It is a divalent group, more preferably a divalent group in which any hydrogen atom in a single bond, acyloxy group, alkylsulfonyl group, acyl group or alkoxycarbonyl group is replaced with a single bond.

When R ^{1a to} R ^13a are a substituent containing an alcoholic hydroxyl group, the number of carbon atoms contained is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4. .
The substituent containing an alcoholic hydroxyl group as R ^{1a to} R ^13a may have two or more alcoholic hydroxyl groups. The number of alcoholic hydroxyl groups having a substituent containing an alcoholic hydroxyl group as R ^{1a to} R ^13a is 1 to 6, preferably 1 to 3, and more preferably 1. preferable.
The number of alcoholic hydroxyl groups contained in the compound represented by the general formula (A1) is 1 to 10 in total, preferably 1 to 6, more preferably 1 in total for R ^{1a to} R ^13a. It is three from.

When R ^{1a to} R ^13a do not contain an alcoholic hydroxyl group, R ^{1a to} R ^13a are each independently a hydrogen atom or a substituent, and any substituent may be used without any particular limitation. Halogen atoms, alkyl groups (including cycloalkyl groups, bicycloalkyl groups, and tricycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups (with heterocyclic groups and Cyano group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (Including anilino group), ammonio group, acylamino group, aminocarboni Ruamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), and other known ones Substituents, for example .

Further, two adjacent ones of R ^{1a to} R ^13a are combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These are further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, Pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring , Phenanthridine ring, acridine ring, Enantororin ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) May also be formed.

When R ^{1a to} R ^13a do not contain an alcoholic hydroxyl group, R ^{1a to} R ^13a are preferably a hydrogen atom or a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group), an alkenyl group. (Including cycloalkenyl group and bicycloalkenyl group), alkynyl group, aryl group, cyano group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino Group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfonyl group, aryloxycarbonyl group, alkoxycarbo Nyl group, carbamoyl group, imide group, silyl group, and ureido group.

When R ^{1a to} R ^13a do not contain an alcoholic hydroxyl group, R ^{1a to} R ^13a are more preferably a hydrogen atom or a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), cyano Group, alkoxy group, acyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl and arylsulfonyl group, alkoxycarbonyl group and carbamoyl group.
Further, when R ^{1a to} R ^13a do not contain an alcoholic hydroxyl group, R ^{1a to} R ^13a are particularly preferably a hydrogen atom or an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), a halogen atom. And an alkoxy group.

In general formula (A1), at least one of R ^{1a to} R ^13a contains an alcoholic hydroxyl group, and preferably at least one of R ^{9 to} R ¹³ contains an alcoholic hydroxyl group.

Za represents a single bond or a divalent linking group, and examples of the divalent linking group include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, A thioether group, an amino group, a disulfide group, an acyl group, an alkylsulfonyl group, —CH═CH—, —C≡C—, an aminocarbonylamino group, an aminosulfonylamino group, and the like, and may have a substituent. . These substituents are the same as the substituents shown for R ^{1a to} R ^13a above. Za preferably has a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, —CH═CH—, —C≡C—, an aminocarbonylamino group, an aminosulfonylamino group, or the like. A substituent, more preferably a single bond, an ether group or a thioether group, particularly preferably a single bond.

The counter anion as X ⁻ in the general formula (A1) is the same as the non-nucleophilic anion as X ⁻ in the acid generator and the acid generator represented by the general formula (ZI ′) or (ZII ′). Can be mentioned.

  The molecular weight of the compound represented by the general formula (A1) is preferably 200 to 2000, and particularly preferably 400 to 1000.

  Specific examples of the compound represented by the general formula (A1) include (A1) to (A36) exemplified in [0095] of US2007 / 0184384A, but are not limited thereto. It is not something. For the synthesis method of the compound represented by the general formula (A1), refer to US2007 / 0184384A.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, when an acid generator is used in addition to the resin (P) having a photoacid generating structure, the acid generator is used alone or in combination of two. The above can be used in combination. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.
The content of the acid generator in the composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and still more preferably based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is 0-7 mass%. The acid generator is not an essential component in the present invention, but is usually used in an amount of 0.01% by mass or more in order to obtain the effect of addition.

<Organic solvent>
Solvents that can be used when preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate Esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may contain rings (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, etc. Mention may be made of organic solvents.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

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

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

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

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

Preferred solvents that can be used include 2-heptanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid Examples include ethyl, ethyl pyruvate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and propylene carbonate. Particularly preferred solvents include propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether.
In the present invention, the above solvents may be used alone or in combination of two or more.

<Surfactant>
The composition of the present invention preferably further contains a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.
Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.
In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] et seq. Of US Patent Application Publication No. 2008 / 0248425A1.

  These surfactants may be used alone or in several combinations.

  The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). is there.

<Acid-decomposable dissolution inhibiting compound>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter referred to as “dissolution inhibiting compound”), which decomposes by the action of an acid and increases the solubility in an alkaline developer. Say).
The dissolution inhibiting compound is preferably an alicyclic or aliphatic compound containing an acid-decomposable group, such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996). . Examples of the acid-decomposable group and alicyclic structure are the same as those described for the acid-decomposable resin.
When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with an electron beam, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.

  The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.

  The addition amount of the dissolution inhibiting compound is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. The dissolution inhibiting compound is not an essential component in the present invention, but is usually used at 0.01% by mass or more in order to obtain the effect of addition.

  Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

<Other ingredients>
In the composition of the present invention, in addition to the components listed above, dyes such as oil dyes and basic dyes from the viewpoint of adjustment of absorbance, photosensitizers known from the viewpoint of sensitivity adjustment, phenolic OH groups, etc. A low molecular dissolution accelerator having a molecular weight of 1,000 or less and having two or more carboxy groups or one or more carboxy groups, a proton acceptor functional group described in JP-A-2006-208781, JP-A-2007-286574, etc. A compound having a group can also be suitably used for the composition of the present application.

<Pattern formation method>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is applied on a support such as a substrate,
An actinic ray-sensitive or radiation-sensitive film is formed. This film thickness is preferably 0.02 to 0.1 μm.

  As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater. Dry to form an actinic ray sensitive or radiation sensitive film. In addition, a known antireflection film can be applied in advance.
The film is irradiated with radiation such as electron beam (EB), X-rays or EUV light, usually through a mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.

In the development step, an alkaline developer is used as follows. Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, di- Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkaline aqueous solutions such as salts, cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

Synthesis Example 1 (Synthesis of Monomer (M-1))
In 80 parts by mass of ethyl acetate, 10 parts by mass of p-hydroxystyrene and 0.01 parts by mass of p-toluenesulfonic acid / pyridine salt were dissolved at room temperature. While stirring this solution, a mixed solution of 6.1 parts by mass of ethyl vinyl ether and 20 parts by mass of ethyl acetate was added dropwise at room temperature. After dropping, the reaction was further allowed to proceed at room temperature for 24 hours.
Triethylamine was added to the reaction solution to make it basic, and after washing with ion exchange water, the organic layer was concentrated and purified by column chromatography with hexane / ethyl acetate to obtain 10.5 mass of the following monomer (M-1). I got a part.

Synthesis Example 2 (Synthesis of monomer (M-2))
In Synthesis Example 1, the reaction was conducted in the same manner as in Synthesis Example 1 except that 10.7 parts by mass of cyclohexyl vinyl ether was used instead of ethyl vinyl ether, and the following monomer (M-2)
Of 12.3 parts by mass.

Synthesis Example 3 (Synthesis of monomer (M-3))
In Synthesis Example 1, the reaction was conducted in the same manner as in Synthesis Example 1 except that 13.1 parts by mass of 2-cyclohexylethyl vinyl ether was used instead of ethyl vinyl ether to obtain 14.7 parts by mass of the following monomer (M-3). It was.

Synthesis Example 4 (Synthesis of monomer (M-4))
In Synthesis Example 1, the reaction was carried out in the same manner as in Synthesis Example 1 except that 20.9 parts by mass of 2- (4-cyclohexylphenoxy) ethyl vinyl ether was used instead of ethyl vinyl ether, and the following monomer (M-4) was added to 19 .3 parts by mass were obtained.

Synthesis Example 5 (Synthesis of monomer (M-5))
The following monomer (M-5) was synthesized by the method described in WO 06/121096 pamphlet.

Synthesis Example 6 (Synthesis of monomer (M-6))
The following monomer (M-6) was synthesized by the method described in US Patent Application Publication No. 2007/0117043.

Synthesis Example 7 (Synthesis of monomer (M-7))
The following monomer (M-7) was synthesized by the method described in US Patent Application Publication No. 2007/0117043.
Synthesis Example 8 (Synthesis of monomer (M-8))
The following monomer (M-8) was synthesized by the method described in WO 06/121096 pamphlet.

Synthesis Example 9 (Synthesis of Resin (P-1))
4.66 parts by mass of 1-methoxy-2-propanol was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, 2.63 parts by mass of 4-hydroxystyrene (hereinafter also referred to as “HOST”), 5.78 parts by mass of the monomer (M-1) obtained in Synthesis Example 1, and the above synthesis example 1.60 parts by weight of the monomer (M-5) obtained in No. 5, 18.6 parts by weight of 1-methoxy-2-propanol, dimethyl 2,2′-azobisisobutyrate [V-601, Wako Pure Chemical Industries, Ltd. )] 1.26 parts by mass of the mixed solution was added dropwise over 2 hours. After completion of dropping, the mixture was further stirred at 80 ° C. for 4 hours. After allowing the reaction solution to cool, 5.5 parts by mass of the resin (P-1) of the present invention was obtained by performing reprecipitation and vacuum drying using a large amount of hexane / ethyl acetate. The weight average molecular weight (Mw: polystyrene conversion) determined from GPC (carrier: N-methyl-2-pyrrolidone (NMP)) is Mw = 13000, Mw / Mn (hereinafter also referred to as “MWD”) = 1.65. there were.

Synthesis Examples 10 to 20 (Synthesis of resins (P-2) to (P-12))
Thereafter, radical polymerization was carried out in the same manner as in Synthesis Example 8 to synthesize resins (P-2) to (P-12) used in the present invention. About resin (P-1)-(P-12) of this invention, each structure, a composition ratio, a weight average molecular weight, and a dispersion degree are shown.

[Examples 1 to 17 and Comparative Examples 1 to 6]
<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in Table 2 below were dissolved in the mixed solvent shown in Table 2, and this was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm, and the total solid content concentration (% by mass) shown in Table 2 was obtained. The actinic ray-sensitive or radiation-sensitive resin composition (positive resist solution) was prepared and evaluated as follows. The concentration (% by mass) of each component described in Table 2 is based on the total solid content.

<Evaluation (EB)>
The prepared actinic ray-sensitive or radiation-sensitive resin composition is uniformly applied onto a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 90 seconds. A film having a thickness of 100 nm was formed.
This film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage: 50 keV). Immediately after irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds. Furthermore, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern. Was evaluated by the following method.
〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 100 nm line (line: space = 1: 1).
[Resolution]
The resolving power was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the irradiation dose showing the above sensitivity.
[Line edge roughness (LER)]
The distance from the reference line where there should be an edge, using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) for any 30 points in the length direction 50 μm of the 100 nm line pattern at the irradiation amount showing the sensitivity described above. Was measured, the standard deviation was obtained, and 3σ was calculated.
[Pattern shape]
The cross-sectional shape of the 100 nm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and three-step evaluation was performed: rectangular, slightly tapered, and tapered.

  The structures of materials (other resins, conventional acid generators, basic compounds) used in Examples and Comparative Examples are shown below.

Surfactants and solvents used in Examples and Comparative Examples are shown below.
W-1: Megafac F176 (Dainippon Ink Chemical Co., Ltd., fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd., fluorine and silicon)
W-3: Polysiloxane polymer (Shin-Etsu Chemical Co., Ltd., silicon-based)
S1: Propylene glycol monomethyl ether acetate (PGMEA)
S2: Propylene glycol monomethyl ether (PGME)

In Comparative Examples 1 and 5, a 100 nm line and space pattern (L / S = 1/1) could not be formed.
From Table 2, it is clear that the actinic ray-sensitive or radiation-sensitive resin composition of the present invention satisfies high sensitivity, high resolution, good pattern shape, and good line edge roughness at the same time.

[Examples 18 to 20]
<Evaluation (EUV light)>
The components shown in Table 3 below were dissolved in the mixed solvent shown in Table 3, and this was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm, and the total solid content concentration (% by mass) shown in Table 3 was obtained. The actinic ray-sensitive or radiation-sensitive resin composition (positive resist solution) was prepared and evaluated as follows. The concentration (% by mass) of each component described in Table 3 is based on the total solid content. The symbols of the compounds described in Table 3 are the same as those in Table 2.
The prepared actinic ray-sensitive or radiation-sensitive resin composition is uniformly applied onto a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 90 seconds. A film having a thickness of 100 nm was formed.
The film was irradiated with an EUV exposure apparatus (manufactured by RISOTEC Japan, wavelength 13 nm), and immediately after irradiation, heated on a hot plate at 110 ° C. for 90 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern (line: space = 1: 1). ) And the obtained pattern was evaluated by the following method.
〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 100 nm line (line: space = 1: 1).
[Pattern shape]
The cross-sectional shape of the 100 nm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and three-step evaluation was performed: rectangular, slightly tapered, and tapered.

  From Table 3, it is clear that the actinic ray-sensitive or radiation-sensitive resin composition of the present invention simultaneously satisfies high sensitivity and good pattern shape even in EUV light.

Claims (10)

A repeating unit (A) having an ionic structure site and decomposing upon irradiation with actinic rays or radiation to generate an acid;
A resin (P) having at least one phenolic hydroxyl group and a repeating unit (B) having a group in which part or all of the hydrogen atoms of the hydroxyl group are protected by a group capable of leaving by the action of an acid. Contains,
The ionic structure site of the repeating unit (A) of the resin (P) has a structure that generates an acid anion in the side chain of the resin upon irradiation with actinic rays or radiation, and the generated acid has a pKa of 0 or less. An actinic ray-sensitive or radiation-sensitive resin composition characterized by the above. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the acid anion has a structure represented by the following general formula (X).

In general formula (X),
Rf ₁ represents any of an alkylene group, a cycloalkylene group, an arylene group, and a combination thereof, at least a part of which is substituted with a fluorine atom or a fluoroalkyl group. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (B) is a repeating unit represented by the following general formula (I).

Here, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₀₃ represents an alkylene group and may be bonded to Ar ₁ to form a 5-membered or 6-membered ring.
Ar ₁ represents an aromatic ring group.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3, wherein Y in the general formula (I) is represented by the following general formula (II).

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group, an alicyclic group which may contain a hetero atom, an aromatic ring group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. .
At least two of Q, M, and L ₁ may combine to form a 5-membered or 6-membered ring. The actinic ray-sensitive or radiation-sensitive property according to any one of claims 1 to 4, wherein the resin (P) further has a repeating unit (C) represented by the following general formula (VI). Resin composition.

Here, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₀₃ represents an alkylene group and may be bonded to Ar ₁ to form a 5-membered or 6-membered ring.
Ar ₁ represents an aromatic ring group.
n represents an integer of 1 to 4.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the resin (P) has a weight average molecular weight in the range of 1000 to 100,000.   The resin (P) has a repeating unit (A) of 0.5 to 80 mol%, a repeating unit (B) of 3 to 90 mol%, and a repeating unit (C) of 3 to 90 mol%. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5 or 6.   Furthermore, a basic compound is contained, The actinic-ray-sensitive or radiation-sensitive resin composition in any one of Claims 1-7 characterized by the above-mentioned.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the composition is for exposure with an electron beam, an X-ray or EUV light.   A pattern forming method comprising: forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, exposing and developing the film.