JP2006091662A - Positive resist composition and method for forming pattern by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist composition having preferable sensitivity, resolution and a pattern profile, small line edge roughness and preferable surface roughness for forming a pattern with active rays or radiation, and to provide a method for forming a pattern by using the composition. <P>SOLUTION: The positive resist composition is provided which contains: (A) a compound which generates an acid by irradiation with active rays or radiation; and (B) a resin having a specified repeating unit, the solubility of which with an alkali developer solution increases by the effect of an acid. The method for forming a pattern by using the above composition is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a positive resist composition used for manufacturing a semiconductor integrated circuit element, a mask for manufacturing an integrated circuit, and the like, and a pattern forming method using the same.

  A chemically amplified positive resist composition, known as a positive resist composition, generates an acid in an exposed area by irradiation with actinic light or radiation such as far ultraviolet light, and a reaction using this acid as a catalyst to generate active light. Or it is a pattern forming material which changes the solubility with respect to the developing solution of a radiation irradiation part and a non-irradiation part, and forms a pattern on a board | substrate.

  The chemically amplified positive resist composition comprises an alkali-soluble resin, a compound that generates an acid upon exposure to actinic rays or radiation (acid generator), and a dissolution inhibiting compound for the alkali-soluble resin having an acid-decomposable group. A three-component system, a resin having a group that decomposes by reaction with an acid and becomes alkali-soluble and a two-component system composed of an acid generator, a resin having a group that decomposes by reaction with an acid and becomes alkali-soluble, an acid It can be roughly classified into a hybrid system comprising a low molecular dissolution inhibiting compound having a degradable group and an acid generator.

Patent Document 1 (Japanese Patent Laid-Open No. 2003-280199) discloses a positive resist composition for an electron beam and EUV light containing an acid-decomposable resin having an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group in the acetal structure. Things are disclosed.
Patent Document 2 (Japanese Patent Laid-Open No. 2003-140361) discloses a resist composition for EUV light containing a (meth) acrylic ester resin.

  However, conventional positive resist compositions have been desired to improve sensitivity, resolution, pattern shape, line edge roughness, and surface roughness.

JP 2003-280199 A JP 2003-140361 A

  The object of the present invention is good in sensitivity, resolving power and pattern shape for pattern formation by actinic rays or radiation, preferably for pattern formation by electron beam, EUV light (Extreme Ultraviolet: near wavelength 13 nm) or X-ray. Another object of the present invention is to provide a positive resist composition having a small line edge roughness and a good surface roughness and a pattern forming method using the same.

  The positive resist composition and the pattern forming method using the same according to the present invention have the following configurations.

(1) (A) a compound that generates an acid upon irradiation with actinic rays or radiation, and (B) at least a repeating unit represented by the following general formula (B1) and a repeating unit represented by the following general formula (B2). A positive resist composition comprising a resin whose solubility in an alkaline developer is increased by the action of an acid.

In general formulas (B1) and (B2),
Z represents a hydroxyl group, a halogen atom, a cyano group, a nitro group, an acyl group, or an acyloxy group.
A ₁ represents a group containing a cyclic carbon structure and decomposing by the action of an acid.
Ra represents a hydrogen atom, a methyl group, a halogen atom, a cyano group, or a trifluoromethyl group.
Re represents a group having a phenol group or a group having a group which is decomposed by the action of an acid to be converted into a phenol group.
m represents an integer of 1 to 3.
n represents an integer of 0 to 2.

(2) In the general formula (B1), -OA ₁ is represented by the following general formula (X1) or (X2), The positive resist composition as described in (1).

In general formulas (X1) and (X2),
R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group.
R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Za represents a cycloalkyl group or an aryl group.
Zb represents a group having a cycloalkyl group or a group having an aryl group.
W represents a divalent linking group.
Y represents a group selected from —O—, —OCO—, —COO—, —NHCO—, —CONH—, —S—, —SO ₂ — and —SO ₃ —.
m represents an integer of 0 to 20.

  (3) In the positive resist composition as described in (1) or (2), the compound of the component (A) is contained in the total solid content of the positive resist composition in the range of 6 to 20% by mass. And a positive resist composition for electron beam, EUV light or X-ray.

(4) A pattern forming method comprising a step of forming a resist film from the positive resist composition according to any one of (1) to (3), exposing the resist film, and developing the resist film.

  According to the present invention, in regard to pattern formation by irradiation with actinic rays or radiation, preferably irradiation with electron beam, EUV light or X-ray, it is excellent in sensitivity and resolving power, and also positive in pattern shape, line edge roughness and surface roughness. Mold resist compositions can be provided.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[1] (A) Compound that generates acid upon irradiation with actinic ray or radiation As a compound (acid generator) that generates acid upon irradiation with actinic ray or radiation that can be used in the present invention, photoinitiation of photocationic polymerization Known compounds that generate acids upon irradiation with actinic rays or radiation used in photo-initiators, photo-initiators for photo-radical polymerization, photo-decoloring agents for dyes, photo-discoloring agents, or microresists, and mixtures thereof It 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.

  Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407. JP, 63-26653, JP, 55-164824, JP, 62-69263, JP, 63-146038, JP, 63-163452, JP, 62-153853, The compounds described in JP-A 63-146029 can be used.

  Furthermore, compounds capable of generating an acid upon irradiation with actinic rays or radiation described in US Pat. No. 3,779,778 and European Patent 126,712 can also be used.

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

In the above general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.

Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (Z1-1), (Z1-2) and (Z1-3) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferable examples of the (ZI) component include compounds (Z1-1), (Z1-2), and (ZI-3) described below.

Compound (Z1-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.

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

  Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkyl or cycloalkylsulfonium compound, and an aryldialkyl or dicycloalkylsulfonium compound.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec. -A butyl group, a t-butyl group, etc. can be mentioned.

  The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Aryl group 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 (Eg, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be included as a substituent. Preferred substituents are an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms, and most preferably an alkyl group having 1 to 4 carbon atoms and 1 carbon atom. It is an alkoxy group of ~ 4. 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.

Alkyl groups R ₂₀₁ to R ₂₀₃ are aryl groups, the same cycloalkyl groups as substituents for a cycloalkyl group, an aryl group, an alkoxy group, a halogen atom, a hydroxyl group or a phenylthio group.

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

  Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.

  Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

  The aliphatic hydrocarbon group in the aliphatic sulfonate anion is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl. Group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, Examples thereof include an eicosyl group, and preferably a cycloalkyl group having 3 to 30 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a boronyl group.

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

  The alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent.

  Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an alkylthio group.

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

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

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

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

  Examples of the aliphatic hydrocarbon group in the aliphatic carboxylate anion include those similar to the aliphatic hydrocarbon group in the aliphatic sulfonate anion.

  Examples of the aromatic group in the aromatic carboxylate anion include the same aromatic groups as in the aromatic sulfonate anion.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylmethyl group.

  The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent include aliphatic groups Examples thereof include the same halogen atom, alkyl group, alkoxy group and alkylthio group as in the sulfonate anion and aromatic sulfonate anion.

  Examples of the sulfonylimide anion include saccharin anion.

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

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

As the non-nucleophilic anion of X ⁻ , an aliphatic sulfonate anion substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group substituted with a fluorine atom A bis (alkylsulfonyl) imide anion and a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom are preferred.
The non-nucleophilic anion of X ⁻ is more preferably a fluorine-substituted aliphatic sulfonate anion having 4 to 8 carbon atoms, particularly preferably a nonafluorobutane sulfonate anion or a perfluorooctane sulfonate anion.

  Next, the compound (Z1-2) will be described.

Compound (Z1-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group not containing an 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 aliphatic hydrocarbon group, more preferably a linear, branched, cyclic 2-oxoalkyl group or alkoxycarbonylmethyl group, most preferably a linear, branched 2- An oxoalkyl group;

The aliphatic hydrocarbon group as R _{201 to} R ₂₀₃ may be a linear or branched alkyl group or a cycloalkyl group, and preferably a linear or branched alkyl group having 1 to 10 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group, and a norbornyl group). As the aliphatic hydrocarbon group, a 2-oxoalkyl group and an alkoxycarbonylmethyl group are more preferable.

  The 2-oxoalkyl group may be linear, branched or cyclic, and preferably includes a group having> C = O at the 2-position of the above alkyl group or cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, butyl group, pentyl 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 compound (Z1-3) is a compound represented by the following general formula (Z1-3), and is a compound 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 each 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, a sulfur atom, An ester bond or 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.

Zc ⁻ represents a non-nucleophilic anion and is the same as the non-nucleophilic anion of X ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a straight chain having 1 to 12 carbon atoms. Examples thereof include a chain or branched alkyl group (for example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group).

Examples of the cycloalkyl group as R _{1c to} R _7c include a cycloalkyl group having 3 to 20 carbon atoms, preferably a cycloalkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group). .

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 one of R _{1c to} R _5c is a straight chain, branched alkyl group, cycloalkyl group, or a straight chain, 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 as the alkyl group and cycloalkyl group as R _{1c to} R _7c , and a 2-oxoalkyl group and an alkoxycarbonylmethyl group are more preferable. preferable.

Examples of the 2-oxoalkyl 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 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 formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group.

The alkyl group represented by R _{204 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).

Cycloalkyl groups R ₂₀₄ to R ₂₀₇ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, 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.

X ⁻ represents a non-nucleophilic anion and is the same as the non-nucleophilic anion of X ^{− in} formula (ZI).

  Moreover, the compound represented by the following general formula (ZIV)-(ZVII) is mentioned as a compound which generate | occur | produces an acid by irradiation of other actinic rays or a radiation.

In the general formulas (ZIV) to (ZVII),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₆ represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Each R independently represents an alkyl group, a cycloalkyl group or an aryl group.
_R207 represents an electron-withdrawing group, and preferably represents a cyano group or a fluoroalkyl group.
R ₂₀₈ represents an alkyl group, a cycloalkyl group, or an aryl group.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, the compounds represented by the general formulas (ZI) to (ZIII) are more preferable.

Among the compounds that generate an acid upon irradiation with actinic rays or radiation, even more preferred are sulfonium salts represented by the general formula (ZI), particularly preferred are sulfonium salts having a carbonyl group, most preferred. in the compound (Z1-2) is a compound or compounds represented by the general formula (Z1-3) with either the 2-oxoalkyl group R ₂₀₁ to R _203. The sensitivity is particularly improved by using a compound having a carbonyl group.

  Specific examples of particularly preferable compounds among the compounds that generate an acid upon irradiation with actinic rays or radiation are given below.

  The addition amount of the acid generator is usually 2 to 25% by mass, preferably 4 to 20% by mass, more preferably 6 to 20% by mass, and particularly preferably 6 to 15% by mass with respect to the total solid content of the resist composition. %.

[2] (B) A resin having at least a repeating unit represented by the general formula (B1) and a repeating unit represented by the general formula (B2), which has increased solubility in an alkali developer by the action of an acid. This positive resist composition has at least a repeating unit represented by the following general formula (B1) and a repeating unit represented by the following general formula (B2), and its solubility in an alkaline developer is increased by the action of an acid. Resin (hereinafter also referred to as “acid-decomposable resin (B)”).

In general formulas (B1) and (B2),
Z represents a hydroxyl group, a halogen atom, a cyano group, a nitro group, an acyl group, or an acyloxy group.
A ₁ represents a group containing a cyclic carbon structure and decomposing by the action of an acid.
Ra represents a hydrogen atom, a methyl group, a halogen atom, a cyano group, or a trifluoromethyl group.
Re represents a group having a phenol group or a group having a group which is decomposed by the action of an acid to be converted into a phenol group.
m represents an integer of 1 to 3.
n represents an integer of 0 to 2.

In the general formula (B1), examples of the halogen atom for Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The acyl group of Z is preferably an acyl group having 1 to 8 carbon atoms, and examples thereof include a formyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a pivaloyl group, and a benzoyl group.
The acyloxy group of Z is preferably an acyloxy group having 2 to 8 carbon atoms. For example, an acetoxy group, a propionyloxy group, a butyllyoxy group, a valeryloxy group, a pivaloyloxy group, a hexanoyloxy group, an octanoyloxy group, a benzoyloxy group, etc. Can be mentioned.

In the general formula (B1), the group containing the cyclic carbon structure of A ₁ and decomposing by the action of an acid (hereinafter also referred to as “acid-decomposable group”) is, for example, —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) (provided that at least one of R ₃₆ , R ₃₇ and R ₃₈ represents a group containing a cyclic carbon structure), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ) ( Provided that at least one of R ₃₆ , R ₃₇ and R ₃₉ represents a group containing a cyclic carbon structure), —COO—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) (provided that R ₃₆ , And at least one of R ₃₇ and R ₃₈ represents a group containing a cyclic carbon structure), —C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) (provided that R ₀₁ , R ₀₂ , R ₃₉ At least one represents a group containing a cyclic carbon structure), -C (R ₀₁ ) (R ₀₂ ) COO-C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) (provided that R ₀₁ , R ₀₂ , R ₃₆ , R ₃₇ , R _At least one of ₃₈ represents a group containing a cyclic carbon structure). The group containing a cyclic carbon structure may be a cyclic hydrocarbon group itself such as a cycloalkyl group, an aryl group, or an aralkyl group, or preferably an alkyl group having 1 to 5 carbon atoms substituted with a cyclic hydrocarbon group. It may be.
R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. R ₃₆ and R ₃₉ 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 alkenyl group, an aralkyl group or an aryl group.

As the alkyl group for R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ , an alkyl group having 1 to 8 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, A hexyl group, 2-ethylhexyl group, an octyl group, etc. can be mentioned.
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 cyclopentyl group, a cyclohexyl group, a cyclobutyl 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, tetocyclo A dodecyl group, an androstanyl group, etc. can be mentioned. 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 and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group. Naphthyl group, anthryl group, 9,10-dimethoxyanthryl group, and the like.
As the aralkyl group of R _{36 to} R ₃₉ , R ₀₁ and R _02, an aralkyl group having 7 to 12 carbon atoms is preferable, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkenyl group represented by 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.
R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may have a substituent. Examples of the substituent that R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, and a carboxy group. , Halogen atom, alkoxy group, aryloxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, cyano group, nitro group Etc.

  As the acid-decomposable group, a 2-adamantylpropyl group is particularly preferable.

In the general formula (B1), -OA ₁ is preferably represented by the following general formula (X1) or (X2).

In general formulas (X1) and (X2),
R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group.
R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Za represents a cycloalkyl group or an aryl group.
Zb represents a group having a cycloalkyl group or a group having an alkyl group.
W represents a divalent linking group.
Y represents a group selected from —O—, —OCO—, —COO—, —NHCO—, —CONH—, —S—, —SO ₂ — and —SO ₃ —.
m represents an integer of 0 to 20.

  The group represented by the general formula (X1) or (X2) preferably has 6 to 40 carbon atoms.

The alkyl group as R ₁ and R ₂ in the general formula (X1) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group. Groups and the like.
At least one of R ₁ and R ₂ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

The alkyl group as R ₃ and R ₄ may be linear or branched. As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl. Group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. As a branched alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like.
The cycloalkyl group as R ₃ and R ₄ preferably has 3 to 30 carbon atoms, more preferably 3 to 20, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl. Group, cyclononyl group, cyclodecanoyl group and the like.

  As an aryl group of Za in general formula (X1), Preferably it is C6-C30, More preferably, it is C6-C20, for example, a phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2 -Methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 3-n-propylphenyl group, 2-n-propylphenyl group, 4-i -Propylphenyl group, 3-i-propylphenyl group, 2-i-propylphenyl group, 4-cyclopropylphenyl group, 3-cyclopropylphenyl group, 2-cyclopropylphenyl group, 4-n-butylphenyl group, 3-n-butylphenyl group, 2-n-butylphenyl group, 4-i-butylphenyl group, 3-i-butylphenyl group, 2-i-butyl Phenyl group, 4-t-butylphenyl group, 3-t-butylphenyl group, 2-t-butylphenyl group, 4-cyclobutylphenyl group, 3-cyclobutylphenyl group, 2-cyclobutylphenyl group, 4- Cyclopentylphenyl group, 4-cyclohexylphenyl group, 4-cycloheptenylphenyl group, 4-cyclooctanylphenyl group, 2-cyclopentylphenyl group, 2-cyclohexylphenyl group, 2-cycloheptenylphenyl group, 2-cycloocta Nylphenyl, 3-cyclopentylphenyl, 3-cyclohexylphenyl, 3-cycloheptenylphenyl, 3-cyclooctanylphenyl, 4-cyclopentyloxyphenyl, 4-cyclohexyloxyphenyl, 4-cyclohept Tenyloxyphenyl group, 4-cyclo Tanyloxyphenyl group, 2-cyclopentyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-cycloheptenyloxyphenyl group, 2-cyclooctanyloxyphenyl group, 3-cyclopentyloxyphenyl group, 3-cyclohexyloxyphenyl Group, 3-cycloheptenyloxyphenyl group, 3-cyclooctanyloxyphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4-n-heptenylphenyl group, 4-n-octa Nylphenyl group, 2-n-pentylphenyl group, 2-n-hexylphenyl group, 2-n-heptenylphenyl group, 2-n-octanylphenyl group, 3-n-pentylphenyl group, 3-n- Hexylphenyl group, 3-n-heptenylphenyl group, 3-n-octanylphenyl Group, 2,6-di-isopropylphenyl group, 2,3-di-isopropylphenyl group, 2,4-di-isopropylphenyl group, 3,4-di-isopropylphenyl group, 3,6-di-t- Butylphenyl group, 2,3-di-t-butylphenyl group, 2,4-di-t-butylphenyl group, 3,4-di-t-butylphenyl group, 2,6-di-n-butylphenyl Group, 2,3-di-n-butylphenyl group, 2,4-di-n-butylphenyl group, 3,4-di-n-butylphenyl group, 2,6-di-i-butylphenyl group, 2,3-di-i-butylphenyl group, 2,4-di-i-butylphenyl group, 3,4-di-i-butylphenyl group, 2,6-di-t-amylphenyl group, 2, 3-di-t-amylphenyl group, 2,4-di-t-amylphenyl group, 3,4- -T-amylphenyl group, 2,6-di-i-amylphenyl group, 2,3-di-i-amylphenyl group, 2,4-di-i-amylphenyl group, 3,4-di-i -Amylphenyl group, 2,6-di-n-pentylphenyl group, 2,3-di-n-pentylphenyl group, 2,4-di-n-pentylphenyl group, 3,4-di-n-pentyl Phenyl group, 4-adamantylphenyl group, 2-adamantylphenyl group, 4-isoboronylphenyl group, 3-isoboronylphenyl group, 2-isobornylphenyl group, 4-cyclopentyloxyphenyl group, 4-cyclohexyloxy Phenyl group, 4-cycloheptenyloxyphenyl group, 4-cyclooctanyloxyphenyl group, 2-cyclopentyloxyphenyl group, 2-cyclohexyloxyphenyl group, -Cycloheptenyloxyphenyl group, 2-cyclooctanyloxyphenyl group, 3-cyclopentyloxyphenyl group, 3-cyclohexyloxyphenyl group, 3-cycloheptenyloxyphenyl group, 3-cyclooctanyloxyphenyl group, 4 -N-pentyloxyphenyl group, 4-n-hexyloxyphenyl group, 4-n-heptenyloxyphenyl group, 4-n-octanyloxyphenyl group, 2-n-pentyloxyphenyl group, 2-n- Hexyloxyphenyl group, 2-n-heptenyloxyphenyl group, 2-n-octanyloxyphenyl group, 3-n-pentyloxyphenyl group, 3-n-hexyloxyphenyl group, 3-n-heptenyloxy Phenyl group, 3-n-octanyloxyphenyl group, 2,6-di-isopropyl Oxyphenyl group, 2,3-di-isopropyloxyphenyl group, 2,4-di-isopropyloxyphenyl group, 3,4-di-isopropyloxyphenyl group, 2,6-di-t-butyloxyphenyl group, 2,3-di-t-butyloxyphenyl group, 2,4-di-t-butyloxyphenyl group, 3,4-di-t-butyloxyphenyl group, 2,6-di-n-butyloxyphenyl group Group, 2,3-di-n-butyloxyphenyl group, 2,4-di-n-butyloxyphenyl group, 3,4-di-n-butyloxyphenyl group, 2,6-di-i-butyl Oxyphenyl group, 2,3-di-i-butyloxyphenyl group, 2,4-di-i-butyloxyphenyl group, 3,4-di-i-butyloxyphenyl group, 2,6-di-t -Amyloxyphenyl group, 2 3-di-t-amyloxyphenyl group, 2,4-di-t-amyloxyphenyl group, 3,4-di-t-amyloxyphenyl group, 2,6-di-i-amyloxyphenyl group, 2,3-di-i-amyloxyphenyl group, 2,4-di-i-amyloxyphenyl group, 3,4-di-i-amyloxyphenyl group, 2,6-di-n-pentyloxyphenyl Group, 2,3-di-n-pentyloxyphenyl group, 2,4-di-n-pentyloxyphenyl group, 3,4-di-n-pentyloxyphenyl group, 4-adamantyloxyphenyl group, 3- Adamantyloxyphenyl group, 2-adamantyloxyphenyl group, 4-isoboronyloxyphenyl group, 3-isoboronyloxyphenyl group, 2-isoboronyloxyphenyl group and the like. Is not limited to substituents other than well above examples it is further substituted as long as it is within the above range.

  The cycloalkyl group of Za may be monocyclic, polycyclic, or bridged. For example, the cycloalkyl group may have a bridged structure. Moreover, these groups may have a substituent. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These cycloalkyls may have a substituent. Specific examples of the alicyclic structure of the cycloalkyl group include cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, and the following structures.

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

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

  Further, the further substituents that the above group may have include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, a methoxy group, an ethoxy group, Hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, benzyl group, phenethyl Group, aralkyl group such as cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, the above alkenyl group, vinyloxy group, Such as propenyloxy group, allyloxy group, butenyloxy group, etc. Rukeniruokishi group, said aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

The Z substituent optionally possessed alicyclic structure cycloalkyl group has as _a is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group or a carbon of 6 to 20 carbon atoms 7-20 Is an aralkyl group. These substituents may further have a substituent.

  Specific examples of the group represented by the general formula (X1) are shown below, but are not limited thereto.

In general formula (X2),
The alkyl group as R ₁ and R ₂ are the same alkyl group as R ₁ and R ₂ in the general formula (X1) and the like.
The divalent linking group as W preferably has 1 to 10 carbon atoms, and includes, for example, a linear, branched or cyclic alkylene group, an arylene group, a heteroarylene group, an aralkylene group, and —S—, —C. (═O) —, —N (R ₇ ) —, —SO—, —SO ₂ —, —CO ₂ —, —N (R ₇ ) SO ₂ — or a divalent combination of two or more of these groups The group can be mentioned. Here, R ₇ can include a hydrogen atom or an alkyl group (specific examples of the alkyl group include those similar to the above R ₁ ).

  In the general formula (X2), the group having a cycloalkyl group of Zb and the group having an aryl group may be a cycloalkyl group itself or an aryl group itself, and preferably substituted with a cycloalkyl group or an aryl group. It may be an alkyl group of 5. Examples of the cycloalkyl group and aryl group of Zb in the general formula (X2) include those similar to the cycloalkyl group and aryl group of Za in the general formula (X1).

In the general formula (X2), at least _one of R ₁ and R ₂ is preferably a linear or branched alkyl group having 2 to 4 carbon atoms.

  Specific examples of the group represented by the general formula (X2) are shown below, but are not limited thereto.

  The benzene ring in the general formula (B1) may further have a hydroxyl group, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group, or the like as a substituent.

  Specific examples of the repeating unit represented by formula (B1) are shown below, but are not limited thereto.

  Examples of the phenol group in the general formula (B2) include a group represented by the following general formula (P1).

  In general formula (P1), n1 represents the integer of 1-5.

  In the general formula (B2), the group having a phenol group of Re may be a phenol group itself, or a phenol group bonded directly or via a divalent linking group, preferably having 1 to 5 carbon atoms. Or an alkyl group of Examples of the divalent linking group include -OCO-.

  In the general formula (B2), examples of the group that is decomposed by the action of an acid and changes to a phenol group include a group represented by the following general formula (P2).

In general formula (P2),
A ₂ represents a group that is decomposed by the action of an acid.
n1 represents the integer of 1-5.

Examples of the group capable of decomposing by the action of an acid of A ₂ (hereinafter, also referred to as “acid-decomposable group”) include: —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R _{37) (OR 39), -} COO-C (R 36) (R 37) (R 38), - C (R 01) (R 02) (OR 39), - C (R 01) (R 02) COO -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) and the like.

R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. R ₃₆ and R ₃₉ 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 alkenyl group, an aralkyl group or an aryl group.

As the alkyl group for R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ , an alkyl group having 1 to 8 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, A hexyl group, 2-ethylhexyl group, an octyl group, etc. can be mentioned.
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 cyclopentyl group, a cyclohexyl group, a cyclobutyl 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, tetocyclo A dodecyl group, an androstanyl group, etc. can be mentioned. 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 and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group. Naphthyl group, anthryl group, 9,10-dimethoxyanthryl group, and the like.
As the aralkyl group of R _{36 to} R ₃₉ , R ₀₁ and R _02, an aralkyl group having 7 to 12 carbon atoms is preferable, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkenyl group represented by 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.
R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may have a substituent. Examples of the substituent that R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, and a carboxy group. , Halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups, and the like.

The acid-decomposable group for A ₂ is particularly preferably a t-butyl group, a t-amyl group, a 2-adamantylpropyl group, a t-butoxycarbonyl group, a t-butoxycarbonylmethyl group, the above general formula (X1), What is shown by (X2) is mentioned.

  In the general formula (B2), the group having a group which is decomposed by the action of an acid of Re to be changed into a phenol group may be a group itself which is decomposed by the action of an acid to be changed into a phenol group, or the action of an acid. The alkyl group having 1 to 5 carbon atoms, which is bonded directly or via a divalent linking group, may be a group which decomposes into a phenol group. Examples of the divalent linking group include -OCO-.

  Hereinafter, specific examples of the repeating unit in which Re in the general formula (B2) is a group having a phenol group will be given, but the present invention is not limited thereto.

In the general formula (B2), specific examples of the repeating unit in which Re is a group having a group which is decomposed by the action of an acid and changes to a phenol group include the above-described specific examples of the repeating unit. And a repeating unit in which the hydrogen atom of the ionic hydroxyl group is substituted with the acid-decomposable group A ₂ .

  Hereinafter, in the general formula (B2), preferred specific examples of the repeating unit in which Re is a group having a group which is decomposed by the action of an acid and changes to a phenol group will be given, but the present invention is not limited thereto. It is not something.

  The acid-decomposable resin (B) may further have a repeating unit represented by the following general formula (B3).

  In the general formula (B3), the benzene ring may further have a hydroxyl group, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group, or the like as a substituent.

The content of the repeating unit represented by the general formula (B1) in the acid-decomposable resin (B) is preferably 10 to 40 mol%, more preferably 15 to 30 mol%, based on all repeating units. .
The content of the repeating unit represented by the general formula (B2) in the acid-decomposable resin (B) is preferably 3 to 30 mol%, more preferably 5 to 20 mol%, based on all repeating units. .
The content of the repeating unit represented by the general formula (B3) in the acid-decomposable resin (B) is preferably 5 to 25 mol%, more preferably 10 to 20 mol%, based on all repeating units. .

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

The acid-decomposable resin (B) can be obtained by synthesizing the corresponding vinyl ether and reacting it with a phenolic hydroxyl group-containing alkali-soluble resin dissolved in a suitable solvent such as tetrahydrofuran by a known method. The reaction is usually carried out in the presence of an acidic catalyst, preferably an acidic ion exchange resin, hydrochloric acid, p-toluenesulfonic acid, or a salt such as pyridinium tosylate. The corresponding vinyl ether can be synthesized from an active raw material such as chloroethyl vinyl ether by a method such as a nucleophilic substitution reaction or can be synthesized using a mercury or palladium catalyst.
As another method, it can also be synthesized by a method of acetal exchange using a corresponding alcohol and vinyl ether. In this case, the substituent to be introduced is given to the alcohol, the vinyl ether is mixed with a relatively unstable vinyl ether such as t-butyl vinyl ether, and the reaction is carried out in the presence of an acid such as p-toluenesulfonic acid or pyridinium tosylate. .

  The weight average molecular weight of the acid-decomposable resin (B) is preferably 3000 to 80000, more preferably 5000 to 50000. The range of molecular weight distribution (Mw / Mn) is 1.01 to 4.0, preferably 1.05 to 3.00. In order to obtain a polymer having such a molecular weight distribution, it is preferable to use a technique such as anionic polymerization or radical polymerization.

  Further, the dispersity (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 3.5, and particularly preferably 1.0 to 3.0. , Heat resistance and image formability (pattern profile, defocus latitude, etc.) are improved.

[3] Polyhydroxy compound The acid-decomposable resin (B) is a cross-linked site in which a polyhydroxy compound is added in the synthesis stage to adjust the alkali dissolution rate and improve the heat resistance, and the polymer main chain is linked with a polyfunctional acetal group. May be introduced.

  The addition amount of the polyhydroxy compound is 0.01 to 10 mol%, preferably 0.05 to 8 mol%, more preferably 0.1 to 5 mol%, based on the number of hydroxyl groups in the resin.

Examples of the polyhydroxy compound include those having 2 to 6 phenolic hydroxyl groups or alcoholic hydroxyl groups, preferably 2 to 4 hydroxyl groups, more preferably 2 or 3 hydroxyl groups. is there.
Specific examples are shown below, but the present invention is not limited thereto.

[4] (C) Fluorine-based and / or silicon-based surfactant The positive resist composition of the present invention further comprises (C) a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based interface). It is preferable to contain any one or two or more of activators and surfactants containing both fluorine atoms and silicon atoms.

  When the positive resist composition of the present invention contains the above-mentioned (C) surfactant, a resist having good sensitivity and resolution and less adhesion and development defects when using an exposure light source of 250 nm or less, particularly 220 nm or less. A pattern can be given.

  As these (C) surfactants, for example, JP-A 62-36663, JP-A 61-226746, JP-A 61-226745, JP-A 62-170950, JP 63-3345, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2002-277862, US Pat. No. 5,405,720. , No. 5,360,692, No. 5,529,881, No. 5,296,330, No. 5,436,098, No. 5,576,143, No. 5,294,511, No. 5,824,451 The following commercially available surfactants can also be used as they are.

  Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

  As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Coalesce, etc. Can.

  (C) 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 positive resist composition (excluding the solvent).

[5] (D) Basic compound The positive resist composition of the present invention preferably contains (D) a basic compound in order to reduce a change in performance over time from exposure to heating.

  Preferable structures include structures represented by the following formulas (A) to (E).

In formulas (A) to (E), R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups, wherein R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring. 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, a hydroxyalkyl group having 1 to 20 carbon atoms, and a 3 to 20 carbon atom. A hydroxycycloalkyl group is preferred.

  These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent an alkyl group or cycloalkyl group having 1 to 20 carbon atoms.

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

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. The compound having a diazabicyclo structure is 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] noner-5-ene, 1,8-diazabicyclo [5,4,0]. Undecar 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.

  These basic compounds are used alone or in combination of two or more. The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of a positive resist composition, Preferably it is 0.01-5 mass%. In order to obtain a sufficient addition effect, 0.001% by mass or more is preferable, and 10% by mass or less is preferable in terms of sensitivity and developability of the non-exposed area.

[6] Organic solvent The positive resist composition of the present invention is used by dissolving each component in a predetermined organic solvent.

  Examples of the organic solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl. Ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc.

  In the present invention, the organic solvent may be used alone or in combination, but it is preferable to use a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group are mixed. . Thereby, the generation of particles during storage of the resist solution can be reduced.

  Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.

Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferable, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate. 2-heptanone is most preferred.

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

  In the manufacture of precision integrated circuit elements, the pattern forming process on the resist film is carried out by applying the positive resist composition of the present invention on a substrate (eg, a transparent substrate such as a silicon / silicon dioxide covering, a glass substrate, an ITO substrate). A good resist pattern can be formed by applying an object, drying, forming a resist film, and then irradiating with an electron beam, EUV light or X-ray, and preferably heating, developing, rinsing and drying. it can.

  The film thickness of the resist film formed by applying and drying the positive resist composition of the present invention on a substrate is preferably 50 to 200 nm. By setting the thickness of the resist film to 50 to 200 nm, it is possible to improve the dry etching resistance and the pattern profile and increase the transmittance of the resist film.

  The film thickness of the resist film can be adjusted by the solid content concentration excluding the solvent of the composition, the preferable solid content concentration is 5 to 18% by mass, the more preferable solid content concentration is 7 to 15% by mass, and the particularly preferable solid content is The partial concentration is 9-14% by mass.

  Examples of the alkaline developer of the positive resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, and n-propylamine. Primary amines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, An aqueous solution of alkalis such as quaternary ammonium salts such as tetraethylammonium hydroxide and choline, cyclic amines such as pyrrole and piperidine, and the like can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution.

  Among these alkaline developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and an aqueous solution of choline are more preferable.

  The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass, and the pH of the alkali developer is usually from 10.0 to 15.0.

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

Synthesis Example 1 (Synthesis of resin (B1))
40 g of 4- (benzyloxyethoxy) styrene, 20 g of p-hydroxystyrene, and 10 g of 2-hydroxyphenethyl methacrylate were dissolved in 300 ml of THF. Under a nitrogen stream, 5 g of V-601 (a polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred to a temperature heated to 65 ° C. After 3 hours, 5 g of V-601 (polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was added again, and the mixture was further reacted at 65 ° C. with stirring for 5 hours. After returning the reaction solution to room temperature, 5 ml of dilute hydrochloric acid was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was neutralized with pyridine and then reprecipitated in 2 L of distilled water to obtain a polymer as a white powder.
After the powder is dissolved in acetone, the low molecular weight component is cut by adding water to precipitate the polymer, and the precipitated viscous polymer is dissolved in acetone and then re-precipitated in water, so that the target resin (B1 ) The weight average molecular weight (GPC) of the resin (B1) was 8000, and the degree of dispersion was 1.35.

  Table 1 below shows the weight average molecular weight, composition ratio, and degree of dispersion of the acid-decomposable resins used in the examples and comparative examples.

  Hereinafter, the structure of the resin (P1) used in the comparative example is shown.

Examples 1 to 12 and Comparative Example 1
(I) Preparation and coating of positive resist As shown in Table 2 below, an acid-decomposable resin, an acid generator, a basic compound and a surfactant are dissolved in propylene glycol monomethyl ether acetate, and the solid content concentration is 8. After preparing a 5 mass% solution, the obtained solution was microfiltered with a membrane filter having a 0.1 μm aperture to obtain a resist solution. This resist solution was applied onto a 6-inch silicon wafer using Tokyo Electron spin coater Mark8 and baked at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 0.30 μm.

(Ii) Formation and Evaluation of Positive Resist Pattern This resist film was irradiated with an electron beam using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). After irradiation, it was baked at 110 ° C. for 90 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds, and dried. The obtained pattern was evaluated by the following method.

〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 0.15 μm line (line: space = 1: 1).

[Resolution]
The resolving power was defined as the limiting resolving power (line and space were separated and resolving) at the irradiation dose showing the above sensitivity.

[Pattern shape]
Using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), observe the cross-sectional shape of the 0.15 μm line pattern at the irradiation dose showing the above sensitivity, and perform a three-step evaluation of rectangular, slightly tapered, and tapered. It was.

[Line edge roughness]
The line width was measured at any 30 points in the length direction of 50 μm of the 0.15 μm line pattern at the irradiation dose showing the above sensitivity, and the variation was evaluated by 3σ.
The evaluation results are shown in Table 2.

Abbreviations in Table 2 are shown below.
[Basic compounds]
E-1: Tri-n-hexylamine E-2: 2,4,6-triphenylimidazole E-3: Tetra- (n-butyl) ammonium hydroxide [Surfactant]
W-1: Fluorosurfactant, MegaFuck F-176 (Dainippon Ink Chemical Co., Ltd.)
W-2: Fluorine / silicone surfactant, MegaFac R08 (Dainippon Ink and Chemicals)
W-3: Silicone surfactant, polysiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

  From Table 2, it can be seen that the positive resist composition of the present invention has high sensitivity and high resolution in pattern formation by electron beam irradiation, and is excellent in pattern shape and line edge roughness.

Examples 13 to 14 and Comparative Example 2
Using the resist compositions of Examples 1 and 2 and Comparative Example 1, resist films were obtained in the same manner as in Example 1. However, the resist film thickness was 0.15 μm. The obtained resist film was subjected to surface exposure using EUV light (wavelength 13 nm) while changing the exposure amount by 0.5 mJ in the range of 0 to 5.0 mJ, and further baked at 110 ° C. for 90 seconds. Thereafter, using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate at each exposure amount was measured to determine the sensitivity.
Next, a sample irradiated with EUV light having an exposure amount equivalent to 1/2 of the sensitivity obtained in the above experiment was prepared, and the resist film surface after developing for 60 seconds with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution Was observed with an AFM (atomic force microscope). The results are shown in Table 3.

  From Table 3, it can be seen that the positive resist composition of the present invention is excellent in sensitivity and surface roughness in property evaluation by irradiation with EUV light.

Claims (4)

(A) A compound that generates an acid upon irradiation with actinic rays or radiation, and (B) an acid having at least a repeating unit represented by the following general formula (B1) and a repeating unit represented by the following general formula (B2) A positive resist composition comprising a resin that increases the solubility in an alkali developer due to.
In general formulas (B1) and (B2),
Z represents a hydroxyl group, a halogen atom, a cyano group, a nitro group, an acyl group, or an acyloxy group.
A ₁ represents a group containing a cyclic carbon structure and decomposing by the action of an acid.
Ra represents a hydrogen atom, a methyl group, a halogen atom, a cyano group, or a trifluoromethyl group.
Re represents a group having a phenol group or a group having a group which is decomposed by the action of an acid to be converted into a phenol group.
m represents an integer of 1 to 3.
n represents an integer of 0 to 2. 2. The positive resist composition according to claim 1, wherein —OA ₁ in the general formula (B1) is represented by the following general formula (X1) or (X2).
In general formulas (X1) and (X2),
R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group.
R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Za represents a cycloalkyl group or an aryl group.
Zb represents a group having a cycloalkyl group or a group having an aryl group.
W represents a divalent linking group.
Y represents a group selected from —O—, —OCO—, —COO—, —NHCO—, —CONH—, —S—, —SO ₂ — and —SO ₃ —.
m represents an integer of 0 to 20.   3. The positive resist composition according to claim 1, wherein the compound of component (A) is contained in the total solid content of the positive resist composition in a range of 6 to 20% by mass, and an electron beam. A positive resist composition for EUV light or X-rays.   A pattern forming method comprising: forming a resist film from the positive resist composition according to claim 1; and exposing and developing the resist film.