JP5504130B2 - Positive actinic ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the composition - Google Patents

Description

  The present invention relates to a positive-type actinic ray-sensitive or radiation-sensitive resin composition, and a resist film and a pattern forming method using the composition. More specifically, the present invention relates to, for example, a positive composition used in a semiconductor manufacturing process such as an IC and a photomask, a circuit board such as a liquid crystal and a thermal head, and other photofabrication processes. The present invention relates to a pattern forming method using a composition. More specifically, the present invention relates to a positive composition suitable when, for example, far ultraviolet rays of 250 nm or less, electron beams, soft X-rays, etc. are used as an irradiation source, and a pattern forming method using the composition.

  In recent years, microfabrication by lithography has been demanded to form ultrafine patterns on the order of several tens of nanometers as integrated circuits are highly integrated. Along with this requirement, there is a tendency to shorten the exposure wavelength 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 addition, microfabrication using a resist composition is not only directly used for manufacturing an integrated circuit, but also recently applied to production of a so-called imprint mold structure (for example, Patent Documents 1 and 2, And non-patent document 1).

  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. Particularly in the ultrafine region of 0.25 μm or less, the 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 these requirements at the same time, and it is necessary to solve these problems.

  As one method for solving these problems, use of a resin having a photoacid generator in a polymer side chain has been studied (see, for example, Patent Documents 3 and 4). Patent Document 3 discloses a resin having a photoacid-generating group and a group whose solubility in an alkaline developer is increased by acid decomposition in the same molecule. Patent Document 4 discloses a resin having a photoacid generator having a specific structure in a polymer side chain.

JP 2004-158287 A JP 2008-162101 A JP 2009-93137 A JP 2008-133448 A

Yoshihiko Hirai (ed.) “Nanoimprint Basics and Technology Development / Application Deployment-Nanoimprint Substrate Technology and Latest Technology Deployment” Frontier Publishing (issued in June 2006)

  An object of the present invention is to provide a positive actinic ray-sensitive or radiation-sensitive resin composition that simultaneously satisfies high sensitivity, high resolution, good pattern shape, and good line edge roughness, and a resist using the same. It is to provide a film and a pattern forming method.

  For example, the present invention is as follows.

  [1] A cationic structure containing a repeating unit (A) that decomposes upon irradiation with actinic rays or radiation to generate an acid, wherein the repeating unit (A) contains a monocyclic or polycyclic nitrogen-containing heterocycle A positive-type actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) comprising:

  [2] The composition according to [1], wherein the cation structure includes an azinium cation.

[3] The composition according to [1] or [2], wherein the cationic structure is represented by the following general formula (AZ).

In the formula, R represents a monovalent substituent.

Represents a monocyclic or polycyclic nitrogen-containing heterocycle.
S ^N represents a substituent. m represents an integer of 0 or more.

  [4] The composition according to any one of [1] to [3], wherein the resin (P) further includes a repeating unit (B) that decomposes by the action of an acid to generate an alkali-soluble group.

[5] The composition according to any one of [1] to [4], wherein the resin (P) further includes a repeating unit represented by the following general formula (IV).

In the formula, R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to Ar ₄ to form a ring, and R ₄₂ in this case represents an alkylene group.
X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or an alkylene group.
Ar ₄ represents a divalent aromatic ring group.
n represents an integer of 1 to 4.

  [6] The repeating unit (A) has a structure in which an acid group is generated in a side chain of the resin (P) by irradiation with the actinic ray or radiation. The composition as described.

  [7] The composition according to any one of [1] to [6], which is exposed to an electron beam, an X-ray or a soft X-ray.

  [8] A resist film formed using the composition according to any one of [1] to [7].

  [9] A pattern comprising forming a film using the composition according to any one of [1] to [7], exposing the film, and developing the exposed film Forming method.

  [10] The method according to [9], wherein the exposure is performed with an electron beam, an X-ray, or a soft X-ray.

  According to the present invention, a positive actinic ray-sensitive or radiation-sensitive resin composition that simultaneously satisfies high sensitivity, high resolution, good pattern shape, and good line edge roughness, and a resist film using the same In addition, a pattern forming method can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the groups and atomic groups that do not explicitly indicate substitution or non-substitution include both those that do not have a substituent and those that have a substituent. For example, an “alkyl group” that does not clearly indicate substitution or unsubstituted is not only an alkyl group that does not have a substituent (unsubstituted alkyl group) but also an alkyl group that has a substituent (substituted alkyl group) Is also included.

<Resin (P)>
The positive-type actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a resin (P). This resin (P) contains a repeating unit (A) that decomposes upon irradiation with actinic rays or radiation to generate an acid.

[Repeating unit (A)]
The repeating unit (A) has a cation structure containing a monocyclic or polycyclic nitrogen-containing heterocycle. As the repeating unit (A), any repeating unit (A) may be used as long as it is configured to generate an acid upon decomposition by irradiation with actinic rays or radiation and has the above-described cation structure. When the resin (P) containing such a repeating unit (A) is used, high sensitivity, high resolution, good pattern shape, and good line edge roughness can be satisfied at the same time.

  The cation structure preferably contains an azinium cation. By adopting such a configuration, high sensitivity, high resolution, good pattern shape, and good line edge roughness can be simultaneously satisfied at a higher level.

  Here, “azinium” means (1) an azine ring (6-membered ring containing a nitrogen atom) in the structure (for example, pyridinium, diazinium, triazinium, etc.), or (2) an azine ring. And one having one or more aromatic rings condensed with an azine ring (for example, quinolinium, isoquinolinium, benzoazinium, naphthazinium, etc.).

The cationic structure is also preferably represented by the following general formula (AZ). By adopting such a configuration, high sensitivity, high resolution, good pattern shape, and good line edge roughness can be simultaneously satisfied at a higher level. In addition, the cation represented by the following general formula (AZ) may be an azinium cation or may not be an azinium cation.

In the formula, R represents a monovalent substituent.

Represents a monocyclic or polycyclic nitrogen-containing heterocycle.
S ^N represents a substituent. m represents an integer of 0 or more.

  The substituent represented by R may be an organic group or an inorganic group. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a substituted carbonyl group, and a substituted sulfonyl group. Each of these groups may have a further substituent.

  The alkyl group represented by R may be linear or branched. The alkyl group preferably has 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms, and still more preferably 1 to 20 carbon atoms. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadadecyl, isopropyl, isobutyl, sec-butyl, t- A butyl group, 1-ethylpentyl group, and 2-ethylhexyl group are mentioned.

  The alkyl group represented by R may have a substituent. That is, R may be a substituted alkyl group. Examples of the substituted alkyl group include a trifluoromethyl group, a phenacyl group, a 1-naphthoylmethyl group, a 2-naphthoylmethyl group, a 4-methylsulfanylphenacyl group, a 4-phenylsulfanylphenacyl group, and 4-dimethyl. Aminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitrophenacyl group, chloromethyl group , Bromomethyl group, 2-chloroethyl group, methoxymethyl group, methoxycarbonylmethyl group, isopropoxymethyl group, butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, acetyloxymethyl Group, methylthiomethyl group, tolylti Methyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetramethylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl Group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group , Methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoyl Til group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenyl Phosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methyl Benzyl group, 1-methyl-1-phen Ruechiru group and, include p- methylbenzyl group.

Examples of the substituent that can be introduced into the alkyl group represented by R include, for example, the monovalent substituents composed of the nonmetallic atoms exemplified below in addition to the substituents described in the description of the substituted alkyl group. Also mentioned. Preferred examples including the above-described substituent include a halogen atom (—F, —Br, —Cl, or —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an amino group, and an acyloxy group. Group, carbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl -N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, carbamoyl group, alkylsulfinyl group, aryls Luffy Group, an alkylsulfonyl group, an arylsulfonyl group, (referred to as a sulfonato group) sulfo group (-SO 3 _H) and its conjugated base group, alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, a phosphono group (-PO ₃ H ₂ ) and its conjugate base group (referred to as phosphonato group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, A heterocyclic group and a silyl group are mentioned.

  Specific examples of the aryl group that can be included in the substituent that can be introduced into the alkyl group represented by R include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group.

  The cycloalkyl group represented by R may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 50 carbon atoms, more preferably 4 to 30 carbon atoms, and still more preferably 5 to 20 carbon atoms. Examples of such a cycloalkyl group include a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group.

  The cycloalkyl group represented by R may have further substituents. As this further substituent, the thing similar to what was demonstrated previously as a substituent which can be introduce | transduced into an alkyl group is mentioned, for example.

  The aryl group represented by R may be monocyclic or polycyclic. This group may be a heteroaryl group. The number of carbon atoms of the aryl group represented by R is preferably 6 to 50, more preferably 6 to 30, and still more preferably 6 to 20. Examples of the aryl group include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a 5-naphthacenyl group, and a 1-indenyl group. , 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentarenyl Group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group Senyl group, Quarter anthracenyl group, Ant Quinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group , A coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, and an ovalenyl group.

  The aryl group represented by R may have a further substituent. As this further substituent, the thing similar to what was demonstrated previously as a substituent which can be introduce | transduced into an alkyl group is mentioned, for example.

  The alkenyl group represented by R may be linear or branched. The alkenyl group preferably has 2 to 50 carbon atoms, more preferably 2 to 30 carbon atoms, and still more preferably 3 to 20 carbon atoms. Moreover, this alkenyl group may have a further substituent.

  Examples of such alkenyl groups include vinyl groups, allyl groups, and styryl groups. Further, examples of the further substituent that the alkenyl group may have include those described above as the substituent that can be introduced into the alkyl group.

  The alkynyl group represented by R may be linear or branched. The alkynyl group preferably has 2 to 50 carbon atoms, more preferably 2 to 30 carbon atoms, and still more preferably 3 to 20 carbon atoms. Moreover, this alkynyl group may have a further substituent.

  Examples of such alkynyl group include ethynyl group, propynyl group, and propargyl group. Further, examples of the further substituent that the alkynyl group may have include those described above as the substituent that can be introduced into the alkyl group.

The substituted carbonyl group represented by R is a group represented by the general formula —CO—R ⁰¹³ . Here, R ⁰¹³ is a group consisting of a monovalent nonmetallic atomic group.

  Examples of the substituted carbonyl group include a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group. Examples of the alkyl group and aryl group in each of these groups include the same groups as those described above as the group represented by R.

The substituted sulfonyl group represented by R is a group represented by the general formula —SO ₂ —R ⁰¹¹ . Here, R ⁰¹¹ is a group consisting of a monovalent nonmetallic atomic group.

  Examples of the substituted sulfonyl group include an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. The sulfamoyl group may have a substituent or may not have a substituent. Moreover, as an alkyl group and an aryl group in each said group, the thing similar to what was demonstrated previously as a group represented by R is mentioned, for example.

  The heterocyclic ring containing a nitrogen atom in general formula (I) may be an aromatic ring or a non-aromatic ring. In addition to the nitrogen atom in the formula, the heterocycle may further contain a heteroatom such as a nitrogen atom, an oxygen atom and a sulfur atom. In addition, as described above, this heterocyclic ring may be monocyclic or polycyclic.

  Examples of such heterocycle include imidazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 2H-pyrrole ring, 3H-indole ring, 1H-indazole, purine ring, isoquinoline ring, 4H-quinolidine ring, Quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, phenanthridine ring, acridine ring, phenanthroline ring, phenazine ring, perimidine ring, triazine ring, benzisoquinoline ring, thiazole ring, thiadiazine ring , An azepine ring, an azocine ring, an isothiazole ring, an isoxazole ring, and a benzothiazole ring. Among these, a pyridine ring or a quinoline ring is particularly preferable.

S ^N represents a substituent as described above. Examples of this substituent include the same as those described above for R. These groups may further have a substituent.

  As described above, m is an integer of 0 or more. The upper limit value of m is equal to the number of atoms that can be substituted with a substituent among the atoms constituting the heterocyclic ring.

X ⁻ represents an anion. X ^- by the anion represented, it will be described in detail later.

The cation represented by the general formula (AZ) is preferably represented by the following general formula (AZ-1) or (AZ-2). That is, the heterocyclic ring containing a nitrogen atom in the general formula (AZ) preferably contains a 6-membered ring or a 5-membered ring.

Where
A represents a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom each independently.
Y each independently represents a substituent. At least two of Y may be bonded to each other to form a ring. p represents an integer of 0 to 5.
Z each independently represents a substituent. At least two of Z may be bonded to each other to form a ring. q represents an integer of 0 to 4.
R has the same meaning as in general formula (AZ).

  In both of the general formulas (AZ-1) and (AZ-2), the number of nitrogen atoms, oxygen atoms, or sulfur atoms in A is preferably 0 to 2, more preferably 0 or 1. .

Specific examples of Y and Z include the same as those described above for ^SN in the general formula (AZ). Each of Y and Z may be bonded to each other to form a ring. That is, the cation represented by the general formula (AZ-1) or (AZ-2) may have a condensed ring structure.

  The ring that can be formed by bonding Y or Z to each other may be an aromatic ring or a non-aromatic ring. Further, this ring may be a heterocycle containing a hetero atom. The ring that Y or Z may be bonded to each other is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and particularly preferably a 6-membered ring.

In addition, the ring that can be formed by bonding Y or Z to each other may have a substituent. Examples of this substituent include the same as those described above for S ^N in the general formula (AZ).

When at least one of A is a nitrogen atom, an oxygen atom or a sulfur atom, the cation represented by the general formula (AZ-1) is represented by the following general formula (AZ-1A) or (AZ-1B) Is more preferable.

  In general formulas (AZ-1A) and (AZ-1B), A represents a nitrogen atom, an oxygen atom or a sulfur atom. Y, p, and R are synonymous with each other in the general formula (AZ-1).

When at least one of A is a nitrogen atom, an oxygen atom or a sulfur atom, the cation represented by the general formula (AZ-2) is more preferably represented by the following general formula (AZ-2A).

  In General Formula (AZ-2A), A represents a nitrogen atom, an oxygen atom, or a sulfur atom. Z, q, and R are synonymous with each other in the general formula (AZ-2).

Specific examples of the cation structure containing a monocyclic or polycyclic nitrogen-containing heterocycle are given below.

  The cation represented by the general formula (AZ) is described in, for example, J. AM. CHEM. SOC. 2004, 126, 14071-14078 or J. AM. CHEM. SOC. 2002, 124, 15225-15238. It can be synthesized by the method.

  The repeating unit (A) preferably has a structure that generates an acid group in the side chain of the resin (P) upon irradiation with actinic rays or radiation. By adopting such a structure, the diffusion of the generated acid is further suppressed, and the resolution and pattern shape can be further improved.

The repeating unit (A) is more preferably a repeating unit represented by the following general formula (I) or general formula (II).

In the general formula (I), R ₁₁ , R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
The alkyl group is a linear or branched alkyl group which may have a substituent, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or n-butyl which may have a substituent. Group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like, and an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, particularly preferably 3 or less carbon atoms. Of the alkyl group.
As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R ₁₁ , R ₁₂ and R ₁₃ are preferred.

Examples of the cycloalkyl group include monocyclic or polycyclic cycloalkyl groups which may have a substituent. 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 particularly preferable.

Preferred substituents in each of the above groups include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, an alkyl group exemplified in R _{11 to} R ₁₃ , and a methoxy group. , Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acetoxy group , Acyloxy groups such as butyryloxy groups, and carboxy groups. In particular, a hydroxyl group and a halogen atom are preferable.

R ₁₁ , R ₁₂ and R ₁₃ in the formula (I) are more preferably a hydrogen atom, an alkyl group or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ) or a hydroxymethyl group (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferred.

X ₁₁ , X ₁₂ and X ₁₃ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), divalent It represents a nitrogen-containing non-aromatic heterocyclic group or a group obtained by combining these.
In —NR—, the alkyl group represented by R is a linear or branched alkyl group which may have a substituent, and is the same as the alkyl group in R ₁₁ , R ₁₂ and R ₁₃ above. An example is given. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.
In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means a non-aromatic heterocyclic group having at least one nitrogen atom, preferably 3 to 8 members, specifically, for example, Examples thereof include a divalent linking group having a structure.

When X ₁₁ is a single bond, R ₁₂ may form a ring with Ar _1, and R ₁₂ in this case represents an alkylene group. X ₁₁ is more preferably a single bond, —COO—, or —CONR— (where R is a hydrogen atom or an alkyl group), and particularly preferably a single bond or —COO—.
X ₁₂ is more preferably a single bond, —O—, —CO—, —SO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group), and a group obtained by combining these, a single bond, —OCO -, - OSO ₂ - is particularly preferred.
X ₁₃ is preferably a single bond, —O—, —CO—, —SO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group), and a group obtained by combining these, more preferably a single bond, —OCO -, - OSO ₂ - is particularly preferred.

L ₁₁ represents a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R May be a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

The alkylene group in L ₁₁ may be linear or branched, and examples thereof include 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 alkylene group is a preferred example. An alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.

Examples of the alkenylene group include a group having a double bond at an arbitrary position of the alkylene group described in the above L ₁₁ .
The cycloalkylene group may be monocyclic or polycyclic, for example, a carbon such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, a diamantanylene group, etc. A cycloalkylene group having a number of 3 to 17 is a preferred example. A cycloalkylene group having 5 to 12 carbon atoms is more preferable, and a cycloalkylene group having 6 to 10 carbon atoms is particularly preferable.

  Examples of the divalent aromatic ring group include an arylene group optionally having a substituent having 6 to 14 carbon atoms such as a phenylene group, a tolylene group, and a naphthylene group, or, for example, thiophene, furan, pyrrole, benzo Mention may be made of divalent aromatic ring groups containing heterocycles such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like.

Specific examples of —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.
L ₁₁ is more preferably a single bond, an alkylene group or a cycloalkylene group, particularly preferably a single bond or an alkylene group.

L ₁₂ represents a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which two or more of these are combined, and these groups include a part or all of hydrogen atoms, Substitution is made with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, or a cyano group. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R May be a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

L ₁₂ is an alkylene group, a divalent aromatic ring group, or a combination thereof, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group in which at least a part or all of them are substituted with fluorine atoms is particularly preferable. L ₁₂ is most preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

The alkylene group for L ₁₂ may be linear or branched, and examples thereof include 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 alkylene group is a preferred example. An alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.
The alkenylene group includes a group having a double bond at an arbitrary position of the alkylene group.

  The cycloalkylene group may be monocyclic or polycyclic, for example, a carbon such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, a diamantanylene group, etc. A cycloalkylene group having a number of 3 to 17 is a preferred example.

Examples of the divalent aromatic ring group include the same groups as the specific examples given for the divalent aromatic ring group as the linking group in L ₁₁ described above.
Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₁₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.
Below, while indicating preferred embodiments of L _12, not particularly limited thereto.

Ar ₁ represents a divalent aromatic ring group or a combination of a divalent aromatic ring group and an alkylene group.
The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, or a thiophene, furan, pyrrole, benzo Preferred examples include divalent aromatic ring groups containing a heterocycle such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

Preferred substituents in each of the above groups include alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, etc., aryl groups such as phenyl groups, and the like mentioned for R _{11 to} R _13. Is mentioned.

  Examples of the group in which the divalent aromatic ring group and the alkylene group are combined include the above-described divalent aromatic ring group and, for example, 1 carbon atom such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Preferred examples include aralkylene groups in which ˜8 alkylene groups (which may be linear or branched) are combined.

Ar ₁ is more preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a phenylene group substituted with a phenylene group, a naphthylene group, a biphenylene group or a phenyl group.

Z ₁ represents a structural moiety that is configured to generate an acid group by being decomposed by irradiation with an actinic ray or radiation, and has a cationic structure including a monocyclic or polycyclic nitrogen-containing heterocyclic ring. This cation structure preferably contains an azinium cation. Moreover, it is also preferable that this cation structure is represented by the said general formula (AZ).
The acid group capable of generating Z ₁ is preferably a sulfonic acid group, an imido acid group, or a methido acid group. More specifically, Z ₁ is preferably represented by the following general formula (ZI), (ZII), or (ZIII).

In the general formulas (ZII) and (ZIII), Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ each independently represent —CO— or —SO ₂ —, more preferably —SO ₂ —. It is.
Rz _1, Rz _2, Rz ₃ independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group. In these groups, an embodiment in which part or all of the hydrogen atoms are substituted with fluorine atoms or fluoroalkyl groups (more preferably perfluoroalkyl groups) is more preferable, and 30 to 100% of the number of hydrogen atoms is substituted with fluorine atoms. The embodiment is particularly preferred.

The alkyl group may be linear or branched. For example, an alkyl having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. A group is mentioned as a preferred example. An alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
As the cycloalkyl group, for example, a cycloalkyl group having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group is preferable, and a cycloalkyl group having 3 to 6 carbon atoms is more preferable.

As the aryl group, an aryl group having 6 to 18 carbon atoms is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and a phenyl group is particularly preferable.
Preferred examples of the aralkyl group include an aralkyl group in which an alkylene group having 1 to 8 carbon atoms and the aryl group are bonded. An aralkyl group in which an alkylene group having 1 to 6 carbon atoms and the aryl group are bonded is more preferable, and an aralkyl group in which an alkylene group having 1 to 4 carbon atoms and the aryl group are bonded is particularly preferable.

Rz ₁ , Rz ₂ , and Rz ₃ are more preferably alkyl groups in which some or all of the hydrogen atoms are substituted with fluorine atoms or fluoroalkyl groups (more preferably perfluoroalkyl groups), and 30 to 100 hydrogen atoms. Alkyl groups in which% is substituted with fluorine atoms are particularly preferred.

In the above general formulas (ZI) to (ZIII), A ⁺ represents a cation structure containing the monocyclic or polycyclic nitrogen-containing heterocycle described above. A ⁺ preferably contains the above-described azinium cation.

A ⁺ is also preferably represented by the general formula (AZ). That is, Z ₁ is more preferably represented by the following general formula (ZI-A), (ZII-A) or (ZIII-A).

Where
R, S ^N , and m are as defined in general formula (AZ).
Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Rz ₁ , Rz ₂ , and Rz ₃ are as defined in general formulas (ZII) and (ZIII).

Examples of the polymerizable monomer unit corresponding to the repeating unit of the general formula (I) are shown below as structures after the cations are released by irradiation with actinic rays or radiation to generate an acid.

Next, general formula (II) will be described.
In the general formula (II), R ₂₁ , R ₂₂ and R ₂₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
The alkyl group is a linear or branched alkyl group which may have a substituent, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or n-butyl which may have a substituent. Group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like, and an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, particularly preferably 3 or less carbon atoms. Of the alkyl group.

As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R ₂₁ , R ₂₂ and R ₂₃ are preferable.

  Examples of the cycloalkyl group include monocyclic or polycyclic cycloalkyl groups which may have a substituent. 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 particularly preferable.

Preferable substituents that each of the above groups may have include the same substituents as those described above for R ₁₁ , R ₁₂ and R ₁₃ .

R ₂₁ , R ₂₂ and R ₂₃ in the formula (II) are more preferably a hydrogen atom, an alkyl group or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ) or a hydroxymethyl group (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferred.

X ₂₁ represents —O—, —S—, —CO—, —SO ₂ —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or these Represents a combined group.

In —NR—, the alkyl group represented by R is a linear or branched alkyl group which may have a substituent, and is the same as the alkyl group in R ₂₁ , R ₂₂ and R ₂₃ above. An example is given. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means a non-aromatic heterocyclic group having at least one nitrogen atom, preferably 3 to 8 members. The structure illustrated in X < ₁₁ > -X < ₁₃ > in Formula (I) is mentioned.

X ₂₁ is more preferably —O—, —CO—, —NR— (R is a hydrogen atom or an alkyl group), or a combination thereof, —COO—, —CONR— (R is a hydrogen atom or Alkyl groups) are particularly preferred.

L ₂₁ represents an alkylene group, an alkenylene group, a cycloalkylene group, or a group obtained by combining two or more thereof. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R Is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent aromatic ring group, or a combination thereof.

Examples of the alkylene group for L ₂₁ include the same as those described above for L ₁₁ .

Examples of the alkenylene group include a group having a double bond at an arbitrary position of the alkylene group described above for L ₂₁ .

Examples of the cycloalkylene group include the same as those described above for L ₁₁ .

Examples of the divalent aromatic ring group as the linking group include those similar to those described above for L ₁₁ .

L ₂₁ represents an alkylene group, a cycloalkylene group, or an alkylene group, a cycloalkylene group (for example, -alkylene group-O-alkylene group-, -alkylene group- through -OCO-, -O-, -CONH-). OCO-alkylene group-, cycloalkylene group-O-alkylene group-, -alkylene group-CONH-alkylene group- and the like are particularly preferable.

X ₂₂ and X ₂₃ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.
Specific examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₂₂ and X ₂₃ are the same as those in X ₂₁ described above, and preferred examples are also the same.
X ₂₂ is more preferably a single bond, —S—, —O—, —CO—, —SO ₂ —, or a combination thereof, and is preferably a single bond, —S—, —OCO—, —OSO _2. -Is particularly preferred.
X ₂₃ is more preferably —O—, —CO—, —SO ₂ —, or a group obtained by combining these, and particularly preferably —OSO ₂ —.

Ar ₂ represents a divalent aromatic ring group or a combination of a divalent aromatic ring group and an alkylene group.
The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, or a thiophene, furan, pyrrole, benzo Preferred examples include divalent aromatic ring groups containing a heterocycle such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

Preferred substituents in each of the above groups are alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, etc., aryl groups, such as phenyl groups, and the like mentioned for R _{21 to} R _23. Is mentioned.

  Examples of the group in which the divalent aromatic ring group and the alkylene group are combined include the above-described divalent aromatic ring group and, for example, 1 carbon atom such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Preferred examples include aralkylene groups in which ˜8 alkylene groups (which may be linear or branched) are combined.

Ar ₂ is preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, an aralkylene group in which an arylene group having 6 to 18 carbon atoms and an alkylene having 1 to 4 carbon atoms are combined, and is preferably a phenylene group A phenylene group substituted with a naphthylene group, a biphenylene group or a phenyl group is particularly preferred.

L ₂₂ represents an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which two or more of these are combined, and these groups each include a part or all of hydrogen atoms, a fluorine atom, Substitution with a substituent selected from a fluorinated alkyl group, a nitro group, or a cyano group. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R May be a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

L ₂₂ is an alkylene group, a divalent aromatic ring group, or a combination of these, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group and a divalent aromatic ring group, in which at least a part or all of them are substituted with a fluorine atom, are particularly preferable. L ₂₂ is most preferably an alkylene group or a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

Examples of the alkylene group for L ₂₂ include the same as those described above for L ₁₁ .

  The alkenylene group includes a group having a double bond at an arbitrary position of the alkylene group.

The cycloalkylene group may be monocyclic or polycyclic, for example, a carbon such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, or a diamantylene group. A cycloalkylene group having a number of 3 to 17 is a preferred example.
Examples of the divalent aromatic ring group include the same groups as the specific examples described for the divalent aromatic ring group as the linking group in L ₂₁ described above.

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₂₂ include the same specific examples as those in X ₂₁ described above, and preferred examples are also the same.
Preferable specific examples of L ₂₂ include the structures exemplified for L ₁₂ in the above general formula (I).

Z ₂ has the same meaning as _{Z 1} in the general formula (I), the above description of _{Z 1} is true for Z _2.

Examples of the polymerizable monomer unit corresponding to the repeating unit of the general formula (II) are shown below as structures after the cations are released by irradiation with actinic rays or radiation to generate an acid.

Further, in another embodiment, the repeating unit (A) is a repeating unit containing an aromatic ring in the side chain excluding the counter anion of the acid anion represented by the general formula (I) or other than the general formula (II). It may be.
The polymerizable monomer unit corresponding to such a repeating unit (A) is exemplified below as a structure after the cation is released by generation of an actinic ray or radiation to generate an acid.

The repeating unit (A) is also preferably represented by the general formula (III).

In the general formula (III), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
The alkyl group is a linear or branched alkyl group which may have a substituent, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or n-butyl which may have a substituent. Group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like, and an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, particularly preferably 3 or less carbon atoms. Of the alkyl group.

As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R ₃₁ , R ₃₂ and R ₃₃ are preferable.

  Examples of the cycloalkyl group include a monocyclic or polycyclic aliphatic hydrocarbon ring group which may have a substituent. 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 particularly preferable.

Preferable substituents that each of the above groups may have include the same substituents as those described above for R ₁₁ , R ₁₂ and R ₁₃ .

R ₃₁ , R ₃₂ and R ₃₃ in the formula (III) are more preferably a hydrogen atom, an alkyl group or a halogen atom, a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ) or a hydroxymethyl group. (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferred.

X ₃₁ and X ₃₂ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.

In —NR—, the alkyl group represented by R is a linear or branched alkyl group which may have a substituent, and is the same as the alkyl group in R ₃₁ , R ₃₂ and R ₃₃ above. An example is given. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.
In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means a non-aromatic heterocyclic group having at least one nitrogen atom, preferably 3 to 8 members. The structure illustrated in X < ₁₁ > -X < ₁₃ > in Formula (I) is mentioned.

X ₃₁ is preferably a single bond, —O—, —CO—, —NR— (wherein R is a hydrogen atom or an alkyl group), or a combination thereof, and —COO—, —CONR— (R is Particularly preferred is a hydrogen atom or an alkyl group.

X ₃₂ is more preferably a single bond, —O—, —CO—, —SO ₂ —, a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining these, a single bond, —OCO— , —OSO ₂ —, a combination of a divalent nitrogen-containing non-aromatic heterocyclic group and —SO ₂ — is particularly preferable.
L ₃₁ represents a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, or a group obtained by combining two or more thereof. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R May be a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

Examples of the alkylene group for L ₃₁ include the same as those described above for L ₁₁ .
Examples of the alkenylene group include a group having a double bond at an arbitrary position of the alkylene group described above for L ₃₁ .

Examples of the cycloalkylene group include the same as those described above for L ₁₁ .

Specific examples of —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group include the same specific examples as in X ₃₁ described above, and preferred examples are also the same.

L ₃₁ is a single bond, an alkylene group, a cycloalkylene group, or a group in which an alkylene group or a cycloalkylene group is combined through —OCO—, —O—, or —CONH— (for example, an —alkylene group—O-alkylene group). Group-, -alkylene group-OCO-alkylene group-, cycloalkylene group-O-alkylene group-, -alkylene group-CONH-alkylene group- and the like are particularly preferable.

L ₃₂ represents an alkylene group, an alkenylene group, a cycloalkylene group, or a group in which two or more of these are combined, and these groups are such that a part or all of the hydrogen atoms are fluorine atoms, fluorinated alkyl groups, nitro groups. Or a substituent selected from a cyano group. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R May be a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

L ₃₂ is more preferably an alkylene group in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group), and part or all of the hydrogen atoms are fluorine atoms. An alkylene group substituted with is particularly preferred. L ₃₂ is most preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

Examples of the alkylene group for L ₃₂ include the same as those described above for L ₁₁ .
The alkenylene group includes a group having a double bond at an arbitrary position of the alkylene group.

The cycloalkylene group may be monocyclic or polycyclic, for example, a carbon such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, or a diamantylene group. A cycloalkylene group having a number of 3 to 17 is a preferred example.
Specific examples of the —NR— linking group and divalent nitrogen-containing non-aromatic heterocyclic group in L ₃₂ include the same specific examples as in X ₃₁ described above, and preferred examples are also the same.
Preferable specific examples of L ₃₂ include the structures exemplified for L ₁₂ in the general formula (I) described above.

Z ₃ has the same meaning as _{Z 1} in the general formula (I), the above description of _{Z 1} is true for _{Z 3.}

The polymerizable monomer unit corresponding to the repeating unit of the general formula (III) is exemplified below as a structure after the cations are released by irradiation with actinic rays or radiation to generate an acid.

The polymerizable compound (M) corresponding to the repeating unit (A) is synthesized, for example, as follows. First, a lithium, sodium or potassium salt of a polymerizable compound having an acid group and a cation hydroxide, bromide or chloride containing a monocyclic or polycyclic nitrogen-containing heterocycle are prepared. Next, these are reacted by a salt exchange method or a method using an ion exchange resin. In this way, a polymerizable compound corresponding to the repeating unit (A) is obtained.
The polymerizable compound having an acid group can be synthesized, for example, by a general sulfonic acid esterification reaction or sulfonamidation reaction. More specifically, for example, after selectively reacting one sulfonyl halide part of a bissulfonyl halide compound with an amine and an alcohol to form a sulfonamide bond or a sulfonate ester bond, the other sulfonyl halide part is formed. The method of hydrolyzing a part is mentioned. Alternatively, the cyclic sulfonic acid anhydride can be obtained by a method of opening a ring with an amine or an alcohol. Alternatively, US Pat. Fluorine Chem. 105 (2000) 129-136; Fluorine Chem. 116 (2002) 45-48 can also be easily synthesized.

Specific examples of the polymerizable compound (M) corresponding to the repeating unit (A) are shown in Table 1 below as combinations of a cation structure and an anion structure.

  Resin (P) may contain only 1 type of repeating unit (A), and may contain 2 or more types of repeating unit (A).

  The content of the repeating unit (A) in the resin (P) is preferably in the range of 0.5 to 80 mol%, more preferably in the range of 1 to 60 mol%, even more preferably with respect to all the repeating units. Is in the range of 3-40 mol%.

[Repeating unit (B)]
The resin (P) is different from the repeating unit (A) and is decomposed by the action of an acid to generate an alkali-soluble group (B) (hereinafter referred to as “a repeating unit having an acid-decomposable group”). May have).

  Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.

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

  A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.

As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, 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 represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group.

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.
As the repeating unit (B), a repeating unit represented by the following general formula (V) is more preferable.

In the general formula (V), R ₅₁ , R ₅₂ and R ₅₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₅₂ may be bonded to L ₅ to form a ring (preferably a 5-membered or 6-membered ring), in which case R ₅₂ represents an alkylene group.
L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.
R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may combine with each other to form a ring. _However, no and _{R 55} and _{R 56} are hydrogen atoms at the same time.

The general formula (V) will be described in more detail.
As the alkyl group of R _{51 to} R ₅₃ in the general formula (V), 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, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 3 or less carbon atoms.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in the above R _{51 to} R ₅₃ .

The cycloalkyl group 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 particularly preferable.

  Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups and the like, and the substituent preferably has 8 or less carbon atoms.

When R ₅₂ is an alkylene group and forms a ring with L ₅ , 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, or an octylene group. Groups. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable.

R ₅₁ and R ₅₃ in Formula (V) are more preferably a hydrogen atom, an alkyl group, or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (—CH ₃ ). _2- OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferable. R ₅₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with L ₅ ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group Particularly preferred are (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), a fluorine atom (—F), a methylene group (forms a ring with L ₅ ), and an ethylene group (forms a ring with L ₅ ). .

Examples of the divalent linking group represented by L _5, an alkylene group, a divalent aromatic ring _{group, -COO-L 1 -, -} O-L 1 -, a group formed by combining two or more of these Etc. Here, L ₁ represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.

L ₅ is preferably a single bond, a group represented by —COO—L ₁ —, or a divalent aromatic ring group. In the case of exposure with an ArF excimer laser, a single bond or —COO—L ₁ — is preferable from the viewpoint of reducing absorption in the 193 nm region. L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene or propylene group.

The alkyl group for R _{54 to} R ₅₆ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Particularly preferred are those having 1 to 4 carbon atoms such as a group, an isobutyl group and a t-butyl group.

The cycloalkyl group represented by R ₅₅ and R _56, preferably one having 3 to 20 carbon atoms, cyclopentyl, may be of monocyclic and cyclohexyl group, norbornyl group, adamantyl group, Polycyclic ones such as a tetracyclodecanyl group and a tetracyclododecanyl group may be used.

The ring formed by combining R ₅₅ and R ₅₆ with each other preferably has 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group. A polycyclic group such as an adamantyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group. When R ₅₅ and R ₅₆ are bonded to each other to form a ring, R ₅₄ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

The monovalent aromatic ring groups represented by R ₅₅ and _{R 56,} preferably has 6 to 20 carbon atoms, for example, a phenyl group, a naphthyl group, and the like. When one of R ₅₅ and R ₅₆ is a hydrogen atom, the other is preferably a monovalent aromatic ring group.

In the case of exposure with an ArF excimer laser, R ₅₅ and R ₅₆ are preferably each independently a hydrogen atom, an alkyl group, or a cycloalkyl group from the viewpoint of reducing absorption in the 193 nm region.

As a method for synthesizing a monomer corresponding to the repeating unit represented by the general formula (V), a general method for synthesizing a polymerizable group-containing ester can be applied and is not particularly limited.
Specific examples of the repeating unit (B) are shown below, but the present invention is not limited thereto.

Moreover, resin (P) may contain the repeating unit represented by the following general formula (VI) as a repeating unit (B), and is especially preferable when exposing with an electron beam or EUV.

In general formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring (preferably a 5-membered or 6-membered ring), in which case R ₆₂ represents an alkylene group.
X ₆ represents a single bond, —COO—, —CONR ₆₄ — (R ₆₄ represents a hydrogen atom or an alkyl group). L ₆ represents a single bond or an alkylene group. Ar ₆ represents a divalent aromatic ring group. Y, when there are a plurality, each independently represents 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.

General formula (VI) will be described in more detail.
As the alkyl group of R _{61 to} R ₆₃ in the general formula (VI), a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, 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.

As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R _{61 to} R ₆₃ are preferable.

The cycloalkyl group may be monocyclic or polycyclic, and is preferably a monocyclic type having 3 to 8 carbon atoms such as a cyclopropyl group, cyclopentyl group or cyclohexyl group which may have a substituent. A cycloalkyl group is mentioned.
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.

If R ₆₂ represents an alkylene group, the alkylene group, preferably a methylene group which may have a substituent group, an ethylene group, a propylene group, butylene group, hexylene group, 1 to 8 carbon atoms such as octylene Can be mentioned.

_-CONR 64 represented by X ₆ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64 in,} the same as the alkyl group of R 61 _{to R 63.}

X ₆ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.

The alkylene group for L ₆ is preferably an alkylene group having 1 to 8 carbon atoms, such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group.

Ar ₆ represents a divalent aromatic ring group. The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, or a thiophene, furan, pyrrole, benzo Preferred examples include divalent aromatic ring groups containing a heterocycle such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group and divalent aromatic ring group may have include the groups represented by R _{51 to} R ₅₃ in the above general formula (V). Specific examples similar to the substituents that may be included are listed.

n is preferably 1 or 2, and more preferably 1.
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 represent an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, 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 represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group.
Ar represents a monovalent aromatic ring 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. 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 monovalent aromatic ring group of R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar is preferably a monovalent aromatic ring group having 6 to 10 carbon atoms, for example, an aryl such as a phenyl group, a naphthyl group or an anthryl group. And a divalent aromatic ring group containing a heterocyclic ring such as a group, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.

The group in which the alkylene group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ and the monovalent aromatic ring group are combined is preferably an aralkyl group having 7 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl. Groups and the like.

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

The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl 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 cycloalkyl 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 cycloalkyl structure may be substituted with a hetero atom such as an oxygen atom.

Each of the groups as R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and an 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. The number of carbon atoms is preferably 8 or less.
As the group Y leaving by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, or a group in which an alkylene group and a monovalent aromatic ring group are combined.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, a monovalent 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 ring (preferably 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, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Preferred examples include a group and an octyl group.

The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms. Specifically, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like are preferable examples. Can do.

The monovalent aromatic ring group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms. Specifically, a phenyl group, a tolyl group, a naphthyl group, an anthryl group and the like are preferable examples. Can be mentioned.

Group formed by combining an alkylene group and a monovalent aromatic ring group represented by L ₁ and L ₂ are, for example, a 6 to 20 carbon atoms, a benzyl group, an aralkyl group such as 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, adamantylene group, etc.), alkenylene group (for example, ethylene group, propenylene group, butenylene group, etc.), divalent aromatic ring group (for example, phenylene group, tolylene group, naphthylene group, etc.), -S-, -O _{-, - CO -, - SO} 2 -, - N (R 0) -, and a divalent linking group formed by combining a plurality of these. R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group). Octyl group, etc.).

The alkyl group as Q is the same as each group as L ₁ and L ₂ described above.
In the cycloalkyl group which may contain a hetero atom as Q and the monovalent aromatic ring group which may contain a hetero atom, an aliphatic hydrocarbon ring group which does not contain a hetero atom and a hetero atom Examples of the monovalent aromatic ring group that does not include the above-described cycloalkyl groups as L ₁ and L ₂ , and monovalent aromatic ring groups, preferably 3 to 15 carbon atoms.

  Examples of the cycloalkyl group containing a hetero atom and the monovalent aromatic ring group containing a hetero atom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, Groups having a heterocyclic structure such as thiadiazole, thiazole, pyrrolidone and the like can be mentioned, but if it is a structure generally called a heterocyclic ring (a ring formed of carbon and a heteroatom, or a ring formed of a heteroatom), these It is not limited to.

Q, M, as a ring which may be formed by combining at least two L _1, Q, M, by combining at least two L _1, for example, a propylene group, to form a butylene group, an oxygen atom In the case of forming a 5-membered or 6-membered ring containing.

Each group represented by L ₁ , L ₂ , M, and Q in the general formula (VI-A) may have a substituent, for example, R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ described above. And those described as the substituent that Ar may have, and the carbon number of the substituent is preferably 8 or less.

  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 (VI) are shown below as preferred specific examples of the repeating unit (B), but the present invention is not limited thereto.

  When the resin (P) contains the repeating unit (B), the content of the repeating unit (B) in the resin (P) of the present invention is 5 to 5 with respect to all the repeating units in the resin (P). The range of 90 mol% is preferable, the range of 10 to 80 mol% is more preferable, and the range of 20 to 70 mol% is particularly preferable.

[Repeating unit (C)]
The resin (P) may further have a repeating unit (C) having a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer.
Examples of the group that decomposes by the action of an alkali developer and increases the dissolution rate in the alkali developer include a lactone structure and a phenyl ester structure.
As the repeating unit (C), a repeating unit represented by the following general formula (AII) is more preferable.

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

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether group, an ester group, a carbonyl group, or a divalent linking group obtained by combining these. Ab is preferably a single bond or a divalent linking group represented by —Ab ₁ —CO ₂ —.
Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cyclohexylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

  V represents a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer. A group having an ester bond is preferable, and a group having a lactone structure is more preferable.

As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in the form to be formed are preferred. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 1 to 8 carbon atoms. , Carboxyl group, halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

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

When the resin (P) contains the repeating unit (C), the content of the repeating unit (C) in the resin (P) is preferably in the range of 0.5 to 80 mol% with respect to all the repeating units, More preferably, it is the range of 1-60 mol%, More preferably, it is the range of 2-40 mol%. One type of repeating unit (C) may be used, or two or more types may be used in combination. By using a specific lactone structure, line edge roughness and development defects are improved.
Although the specific example of the repeating unit (C) in resin (P) is shown below, this invention is not limited to this. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Repeating unit (D)]
The resin (P) of the present invention preferably has a repeating unit (D) having an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, a hexafluoroisopropanol group) in which the α-position is substituted with an electron withdrawing group. .

  In the case of exposing with an ArF excimer laser, it is more preferable to have a repeating unit having a carboxyl group. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain. Both are preferable, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

As for the content rate of the repeating unit which has an alkali-soluble group, 1-20 mol% is preferable with respect to all the repeating units in resin (P), More preferably, it is 1-15 mol%, More preferably, it is 1-10 mol%.
Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

In the case of exposure with KrF excimer laser light, electron beam, X-ray, or high energy light (EUV, etc.) having a wavelength of 50 nm or less, an alkali-soluble group having an aromatic ring group is preferable. The structure represented is more preferred. The present inventors have found that the sensitivity of the composition according to the present invention can be further improved by combining the repeating unit (A) with the repeating unit represented by the general formula (IV). Although the reason for this is not necessarily clear, the present inventors have found that the chain reaction described in J. Org. Chem. 2005, 70, 6809-6819 tends to occur, so that the acid from the repeating unit (A) can be obtained. It is presumed that this is because the amount of generation increases.

Here, R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to Ar 4 to form a ring (preferably a 5-membered or 6-membered ring), and R ₄₂ in this case represents an alkylene group.
X ₄ represents a single bond, —COO—, —CONR ₆₄ — (R ₆₄ represents a hydrogen atom or an alkyl group).
L ₄ represents a single bond or an alkylene group.
Ar ₄ represents a divalent aromatic ring group. n represents an integer of 1 to 4.
Specific examples of the alkyl group, cycloalkyl group, halogen atom, and alkoxycarbonyl group of R ₄₁ , R ₄₂ , and R ₄₃ in formula (IV) and the substituent that these groups may have include those in general formula (V). Specific examples similar to the respective groups are given.

The divalent aromatic ring group as Ar ₄ may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or, for example, Preferred examples include divalent aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

Preferable substituents in the above groups are alkoxy groups such as alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups and the like mentioned as R _{51 to} R ₅₃ in formula (V). And aryl groups such as a phenyl group.

_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64 in,} the same as the alkyl group of R 61 _{to R 63.}

X ₄ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.

The alkylene group for L ₄ is preferably an alkylene group having 1 to 8 carbon atoms, such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group.

Ar ₄ is more preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a phenylene group, a naphthylene group, or a biphenylene group.

  Specific examples of the repeating unit having an aromatic ring group and an alkali-soluble group are shown below, but the present invention is not limited thereto. In formula, a represents the integer of 0-2.

  The content of the repeating unit having an alkali-soluble group represented by the general formula (IV) is preferably from 3 to 90 mol%, more preferably from 5 to 80 mol%, still more preferably based on all repeating units in the resin (P). Is 7-70 mol%.

Although the specific example of the repeating unit which has an alkali-soluble group represented by general formula (IV) below is shown, this invention is not limited to this. In formula, a represents the integer of 0-2.

[Other repeat units]
Resin (P) is a repeating unit other than the repeating units described above, and may further have a repeating unit having a hydroxyl group or a cyano group. As a result, substrate adhesion and developer compatibility can be improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferable.

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

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

In the general formulas (AIIa) to (AIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c.

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

The resin (P) of the present invention can further have a repeating unit that has an alicyclic hydrocarbon structure having no polar group and does not exhibit acid decomposability. An example of such a repeating unit is a repeating unit represented by the general formula (VII).

In general formula (VII), R ₅ represents a hydrocarbon group having at least one alicyclic hydrocarbon structure and having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

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

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

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

  These alicyclic hydrocarbon groups may have a substituent, and preferable substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. . Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and examples of the substituent that may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protective group, and an amino group protected with a protective group Can be mentioned.

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

  The content of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability is preferably 1 to 40 mol%, more preferably based on all repeating units in the resin (P). 1 to 20 mol%.

Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (P) of the present invention has, in addition to the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties of resist, resolving power, heat resistance, sensitivity. Various repeating structural units can be included for the purpose of adjusting the etc.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, performance required for the resin used in the composition of the present invention, in particular, (1) solubility in coating solvent, (2) film-forming property (glass transition point), (3) alkali developability, (4 Fine adjustments such as ()) film slippage (selection of hydrophilicity / hydrophobicity, alkali-soluble group), (5) adhesion of unexposed part to substrate, (6) dry etching resistance, etc. are possible.

As such monomers, for example, addition polymerization selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic esters, and the like. Examples include compounds having one unsaturated bond.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin (P) used in the composition of the present invention, the content molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist requirements. It is appropriately set in order to adjust the resolution, heat resistance, sensitivity, etc., which are performance.

The form of the resin (P) of the present invention may be any of random type, block type, comb type, and star type.
The resin (P) can be synthesized, for example, by radical, cation, or anionic polymerization of an unsaturated monomer corresponding to each structure. It is also possible to obtain the desired resin by polymerizing after using an unsaturated monomer corresponding to the precursor of each structure and then performing a polymer reaction.

  For example, as a general synthesis method, an unsaturated monomer and a polymerization initiator are dissolved in a solvent, and a batch polymerization method in which polymerization is performed by heating, a solution of an unsaturated monomer and a polymerization initiator in a heating solvent for 1 to 10 hours. The dropping polymerization method etc. which are dropped and added over are mentioned, and the dropping polymerization method is preferable.

  Examples of the solvent used for the polymerization include a solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition described below, and more preferably the composition of the present invention. Polymerization is preferably carried out using the same solvent as used in the above. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

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

The reaction concentration is 5 to 70% by mass, preferably 10 to 50% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 40 ° C to 100 ° C.
The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, more preferably 1 to 12 hours.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

  In addition, once the resin is precipitated and separated, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

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

  The molecular weight of the resin (P) according to the present invention is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 60000, and in the range of 2000 to 30000. It is particularly preferred. By setting the weight average molecular weight in the range of 1000 to 100,000, it is possible to prevent heat resistance and dry etching resistance from being deteriorated, and also to prevent developability from being deteriorated and the film forming property from being deteriorated due to increased viscosity. be able to. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

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

  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 especially preferable.

Specific examples of the resin (P) are shown below, but the present invention is not limited to these.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, if necessary, a resin that decomposes by the action of an acid to increase the dissolution rate in an alkaline aqueous solution, and generates an acid upon irradiation with an actinic ray or radiation. Compound (low molecular photoacid generator (conventional type)), basic compound, low molecular compound having a group capable of leaving by the action of acid, surfactant, acid stronger than carboxylic acid decomposed by the action of acid The substance etc. which produce | generate can be contained.

<Resin that decomposes by the action of an acid and increases the dissolution rate in an aqueous alkali solution>
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 in an alkaline aqueous solution.
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 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 is possible to obtain an alkali-soluble resin monomer having a group capable of being decomposed or reacting with an acid-decomposable group by copolymerization 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 the same as the acid-decomposable group described in the resin (P) of the present invention (for example, the acid-decomposable group described as the repeating unit (B) in the resin (P)). A group can be mentioned as a preferred 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 17 nm / second or more as measured with 2.38 mass% tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 33 nm / second or more.
The content ratio of the group capable of decomposing with an acid is the number of repeating units (X) having a group capable of decomposing with an acid in the resin (X) and the number of repeating units having an alkali-soluble group not protected with a group capable of leaving with an acid. With (Y), it is expressed as X / (X + Y). 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 preferred ranges of molecular weight and dispersity of the acid-decomposable resin are the same as those of the resin (P).
Two or more acid-decomposable resins may be used in combination.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the mixing ratio 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%.

<Compound that generates acid upon irradiation with actinic ray or radiation (low molecular photoacid 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. A low molecular weight compound (hereinafter also referred to as “acid generator” or “photoacid generator”) may be contained.

  Examples of such an acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or an actinic ray or radiation used for a microresist. A known compound that generates an acid by irradiation and a mixture thereof can be appropriately selected and used.

  Examples thereof include azinium salts, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates. Specific examples thereof include those described in [0164] to [0248] of US Patent Application Publication No. 2008 / 0241737A1.

  Further, as the low-molecular photoacid generator, a salt containing a cation containing the monocyclic or polycyclic nitrogen-containing heterocycle described above and an arbitrary anion may be used.

  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. 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 0 to 7% by mass, based on the total solid content of the composition of the present invention. is there. 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.

<Basic compound>
The actinic ray-sensitive or radiation-sensitive composition of the present invention preferably contains a basic compound.

The basic compound is preferably a nitrogen-containing organic basic compound.
Although the compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(4) is used preferably.
(1) Compound represented by the following general formula (BS-1)

In general formula (BS-1),
Each R independently represents a hydrogen atom, an alkyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, or an aralkyl group. However, not all three Rs are hydrogen atoms.
Although carbon number of the alkyl group as R is not specifically limited, Usually, 1-20, Preferably it is 1-12.
Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, 3-20, Preferably it is 5-15.
Although carbon number of the aryl group as R is not specifically limited, Usually, 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, 7-20, Preferably it is 7-11. Specific examples include a benzyl group.
In the alkyl group, cycloalkyl group, aryl group or aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.
In the compound represented by the general formula (BS-1), it is preferable that only one of three Rs is a hydrogen atom, or it is preferable that all Rs are not hydrogen atoms.

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

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

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

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

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

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group has a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound. The phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.

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

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

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

(5) Compound whose basicity is increased by the action of an acid A compound whose basicity is increased by the action of an acid can also be used as one kind of basic compound. As this example, what has a structure represented, for example by the following general formula (A) is mentioned. The following compound has an electron-withdrawing ester bond adjacent to the N atom, so that the basicity is low as it is. However, when an acid acts on the following compound, first, -C (Rb) (Rb) (Rb) Since the site is decomposed and then the ester bond site is decarboxylated, the electron withdrawing ester bond site is removed, so that it is considered that substantial basicity is developed.

In the general formula (A), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.
Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. However, in —C (Rb) (Rb) (Rb), three Rb's are not hydrogen atoms at the same time.

At least two Rb's may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

  In general formula (A), the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Ra and Rb are functional groups such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group and an oxo group, It may be substituted with an alkoxy group or a halogen atom.

The alkyl group, cycloalkyl group, aryl group or aralkyl group of Ra and Rb (these alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted with the above functional group, alkoxy group or halogen atom). ), For example,
Groups derived from linear and branched alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., and groups derived from these alkanes such as cycloalkyl A group substituted by a group,
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, groups derived from these cycloalkanes, for example, substituted with linear or branched alkyl groups Group,
A group derived from an aromatic compound such as benzene, naphthalene, anthracene, a group obtained by substituting a group derived from these aromatic compounds with, for example, a linear or branched alkyl group,
Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole, benzimidazole, and groups derived from these heterocyclic compounds are linear or branched A group substituted with a group derived from an aromatic compound or a group derived from an aromatic compound, a group derived from a linear or branched alkane, or a group derived from a cycloalkane, for example, a group derived from an aromatic compound Or a group in which the above substituent is substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, or an oxo group.

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

Although the compound which basicity increases by the effect | action of the acid especially preferable in this invention is shown concretely, this invention is not limited to this.

The compound represented by the general formula (A) can be easily synthesized from a commercially available amine by a method described in Protective Groups in Organic Synthesis Fourth Edition. As the most general method, there is a method obtained by reacting a dicarbonate or haloformate with a commercially available amine. In the formula, X represents a halogen atom.

Other examples that can be used in the composition of the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, compounds described in paragraph 0108 of JP-A No. 2007-298869, and the like.
A basic compound is used individually or in combination of 2 or more types.
The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of a composition, Preferably it is 0.01-5 mass%.

The molar ratio of acid generator / basic compound is preferably 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. This molar ratio is more preferably 5.0 to 200, and still more preferably 7.0 to 150.
The acid generator in the above molar ratio is the total amount of the repeating unit (a) contained in the resin (P) and the acid generator other than the resin (P) described above.

<Low molecular compound having a group capable of decomposing by the action of acid or alkali>
The composition of the present invention can contain a low molecular weight compound having a group that decomposes by the action of an acid or alkali (except for the above-described compound that increases basicity by the action of an acid). The group that decomposes by the action of an acid or alkali is not particularly limited, but an acetal group, carbonate group, carbamate group, tertiary ester group, tertiary hydroxyl group, hemiaminal ether group, or lactone structure is preferable, and a carbamate group, hemamiamide is preferable. A nal ether group is particularly preferred.

When irradiating with an electron beam or EUV light, what contains the structure which substituted the phenolic hydroxyl group of the phenol compound by the acid-decomposable group is preferable. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.
Specific examples are shown below, but the present invention is not limited thereto.

  As the low molecular weight compound having a group capable of decomposing by the action of acid or alkali, a commercially available product or a compound synthesized by a known method may be used.

<Surfactant>
The composition of the present invention may further contain a surfactant. When contained, the surfactant is preferably a fluorine-based and / or silicon-based surfactant.
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.
Surfactants may be used alone or in combination of two or more.

  The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, based on the total solid content (total amount excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. %, Particularly preferably 0.0005 to 1% by mass.

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

<Solvent>
The solvent that can be used in preparing the composition is not particularly limited as long as it dissolves each component. For example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, cyclic lactone, Examples thereof include linear or cyclic ketone, alkylene carbonate, alkyl carboxylate, alkyl alkoxyacetate, alkyl pyruvate and the like. Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

  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-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of chain or cyclic ketones 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, 3-pentene- -One, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4- Methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone are preferred Can be mentioned.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
As alkyl carboxylate, butyl acetate is mentioned preferably, for example.

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

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

  The content of the solvent in the composition of the present invention can be appropriately adjusted according to the desired film thickness and the like, but generally the total solid content concentration of the composition is 0.5 to 30% by mass, preferably It is prepared so that it may become 1.0-20 mass%, More preferably, it is 1.5-10 mass%.

<Substance that decomposes by the action of acid to produce an acid stronger than carboxylic acid>
The composition of the present invention may contain a substance that decomposes by the action of an acid to produce an acid stronger than a carboxylic acid (hereinafter also referred to as “acid proliferating agent”).
The acid produced from the acid proliferating agent is preferably one having a high acid strength. Specifically, the acid dissociation constant (pKa) is preferably 3 or less, more preferably 2 or less. The acid generated from the acid proliferating agent is preferably sulfonic acid.

Examples of the acid proliferating agent include International Publication No. 95/29968, International Publication No. 98/24000, Japanese Unexamined Patent Publication No. 8-305262, Japanese Unexamined Patent Publication No. 9-34106, Japanese Unexamined Patent Publication No. 8-248561, No. 8-503082, U.S. Pat. No. 5,445,917, JP-T-8-503081, U.S. Pat. No. 5,534,393, U.S. Pat. No. 5,395,736 US Pat. No. 5,741,630, US Pat. No. 5,334,489, US Pat. No. 5,582,956, US Pat. No. 5,578,424, US Patent No. 5,453,345, US Pat. No. 5,445,917, European Patent 665,960, European Patent 757,628, European Patent 665,961 Light U.S. Pat. No. 5,667,943, JP-A-10-1508, JP-A-10-282642, JP-A-9-512498, JP-A-2000-62337, JP-A-2005-2005. The acid proliferating agents described in Japanese Patent No. 17730, Japanese Patent Application Laid-Open No. 2008-209889, and the like can be used alone or in combination of two or more.
Specifically, compounds represented by the following general formulas (1) to (6) are preferable.

In the general formulas (1) to (6),
R represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.

R ₀ represents a group capable of leaving by the action of an acid.
R ₁ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group.
R ₂ represents an alkyl group or an aralkyl group.
R ₃ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ₄ and R ₅ each independently represents an alkyl group, and R ₄ and R ₅ may be bonded to each other to form a ring.

R ₆ represents a hydrogen atom or an alkyl group.
R ₇ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ₈ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.

R ₉ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ₉ may combine with R ₇ to form a ring.
R ₁₀ represents an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group or an alkenyloxy group.
R ₁₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group or an alkenyl group.
R ₁₀ and R ₁₁ may combine with each other to form a ring.
R ₁₂ represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group or a cyclic imide group.

  In the general formulas (1) to (6), examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, and examples of the cycloalkyl group include monocyclic or polycyclic groups having 4 to 10 carbon atoms. Examples of the aryl group include aryl groups having 6 to 14 carbon atoms, examples of the aralkyl group include aralkyl groups having 7 to 20 carbon atoms, and examples of the alkoxy group include carbon atoms. Examples include 1 to 8 alkoxy groups. Examples of alkenyl groups include alkenyl groups having 2 to 6 carbon atoms. Examples of aryloxy groups include aryloxy groups having 6 to 14 carbon atoms. Examples of alkenyloxy groups include alkenyloxy groups. Includes an alkenyloxy group having 2 to 8 carbon atoms.

  Each of the above substituents may further have a substituent, and examples of the substituent include the following. That is, halogen atoms such as Cl, Br, and F, -CN group, -OH group, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, and alkoxy group having 1 to 4 carbon atoms , Acylamino groups such as acetylamino group, aralkyl groups such as benzyl group and phenethyl group, allyloxyalkyl groups such as phenoxyethyl group, alkoxycarbonyl groups having 2 to 5 carbon atoms, acyloxy groups having 2 to 5 carbon atoms, etc. Can be mentioned.

Examples of the ring formed by combining R ₄ and R ₅ with each other include a 1,3-dioxolane ring and a 1,3-dioxane ring.
Examples of the ring formed by combining R ₇ and R ₉ with each other include a cyclopentyl ring and a cyclohexyl ring.
Examples of the ring formed by combining R ₁₀ and R ₁₁ with each other include a 3-oxocyclohexenyl ring and a 3-oxoindenyl ring which may contain an oxygen atom in the ring.

Examples of the group capable of leaving by the action of an acid of R ₀ include tertiary alkyl groups such as t-butyl group and t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-iso 1-alkoxyethyl group such as butoxyethyl group, 1-cyclohexyloxyethyl group, alkoxymethyl group such as 1-methoxymethyl group, 1-ethoxymethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl group, 3 -Oxocyclohexyl group etc. can be mentioned.

Preferred examples of each of R, R ₀ and R _{1 to} R ₁₁ include the following.
R: methyl group, ethyl group, propyl group, butyl group, octyl group, trifluoromethyl group, nonafluorobutyl group, heptadecafluorooctyl group, 2,2,2-trifluoroethyl group, phenyl group, pentafluorophenyl Group, methoxyphenyl group, toluyl group, mesityl group, fluorophenyl group, naphthyl group, cyclohexyl group, camphor group.

_R0 : t-butyl group, methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, tetrahydropyranyl group.

R ₁ ; methyl group, ethyl group, propyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, propoxy group, phenoxy group, naphthoxy group.

R ₂ : methyl group, ethyl group, propyl group, butyl group, benzyl group.

R ₃ : methyl group, ethyl group, propyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, naphthylmethyl group.

R ₄ , R ₅ : Methyl group, ethyl group, propyl group, those bonded to each other to form an ethylene group or a propylene group.

R ₆ : hydrogen atom, methyl group, ethyl group.

R ₇ , R ₉ ; hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, bonded to each other Forming a cyclopentyl ring or a cyclohexyl ring.

R ₈ ; methyl group, ethyl group, isopropyl group, t-butyl group, neopentyl group, cyclohexyl group, phenyl group, benzyl group.

R ₁₀ : methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, methoxy group, ethoxy group, phenyl group, naphthyl group, benzyl group, phenoxy group, naphthoxy Group formed by forming a 3-oxocyclohexenyl ring or a 3-oxoindenyl ring, which may be bonded to each other to contain an oxygen atom.

R ₁₁ : methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, methoxy group, ethoxy group, phenyl group, naphthyl group, benzyl group, phenoxy group, naphthoxy A group formed by forming a 3-oxocyclohexenyl ring or a 3-oxoindenyl ring, which may be bonded to each other to contain an oxygen atom.

In the general formula (6), when R ₁₂ represents an alkyl group, a linear alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 3 to 12 carbon atoms are more preferable.

When R ₁₂ represents a cycloalkyl group, a monocyclic or polycyclic monovalent aliphatic hydrocarbon ring group having 5 to 10 carbon atoms is more preferable.

When R ₁₂ represents a substituted alkyl group or a substituted aliphatic hydrocarbon ring group, a monovalent nonmetallic atomic group excluding hydrogen is used as the substituent, and a preferred example is a halogen atom (—F , -Br, -Cl, -I), alkoxy group, aryloxy group, alkylthio group, arylthio group, N-alkylamino group, N, N-dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-ary Rucarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N- Alkyl-N-arylcarbamoyl, sulfo, sulfonate, sulf Amoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkylphosphono Group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group, phosphonooxy group, phosphonatoxy group, aryl group, alkenyl group and the like.

When R ₁₂ represents an aryl group, examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are more preferable. The aryl group includes a heterocyclic (hetero) aryl group in addition to the carbocyclic aryl group. Examples of the heterocyclic aryl group include those having 3 to 20 carbon atoms and 1 to 5 hetero atoms such as a pyridyl group, a furyl group, and other quinolyl groups condensed with a benzene ring, a benzofuryl group, a thioxanthone group, and a carbazole group. Can be mentioned.

When R ₁₂ represents a substituted aryl group, as the substituted aryl group, those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. Examples of preferable substituents include those shown as the substituents in the aforementioned alkyl group and cycloalkyl group.

When R ₁₂ represents an alkenyl group, a substituted alkenyl group [—C (R ₁₄ ) ═C (R ₁₅ ) (R ₁₆ )], an alkynyl group, or a substituted alkynyl group [—C≡C (R ₁₇ )] As R _{14 to} R ₁₇ , a monovalent nonmetallic atomic group can be used. Preferable examples of R _{14 to} R ₁₇ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those shown as the above examples. More preferable substituents for R _{14 to} R ₁₇ include a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms.

When R ₁₂ represents a cyclic imide group, examples of the cyclic imide include those having 4 to 20 carbon atoms such as succinic imide, phthalic imide, cyclohexane dicarboxylic imide, norbornene dicarboxylic imide and the like.
Specific examples of the compounds represented by the general formulas (1) to (6) include, for example, compounds (1-1) to (1-11) exemplified after [0215] of JP-A-2008-209889. , (2-1) to (2-6), (3-1) to (3-6), (4-1) to (4-7), (5-1) to (5-4), ( 6-1) to (6-20).

<Other ingredients>
In addition to the components described above, the composition of the present invention comprises a carboxylic acid onium salt, a dissolution inhibiting compound having a molecular weight of 3000 or less, a dye, a plasticizer, a photosensitizer described in Proceeding of SPIE, 2724, 355 (1996), etc. Sensitizers, light absorbers and the like can be appropriately contained.

[Pattern formation method]
The composition of the present invention is typically used by dissolving the above-described components in a solvent, filtering the solution, and applying the solution to a support.
The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less.
The thickness of the film is not particularly limited, but is preferably 0.01 to 0.2 μm, and more 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.

The composition is applied by a suitable application method such as a spinner onto a substrate (eg, silicon / silicon dioxide coating) used for manufacturing an integrated circuit element, a photomask, an imprint mold, and the like. Thereafter, it is dried to form a photosensitive film.
The film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common.

  For details on producing an imprint mold structure by applying the composition of the present invention, for example, the basics of nanoimprint and technological development / application development-Nanoimprint substrate technology and latest technological development-Editing : Yoshihiko Hirai Frontier Publishing (issued in June 2006), Japanese Patent No. 4109085, Japanese Patent Application Laid-Open No. 2008-162101, and the like.

  Although it does not specifically limit as actinic light or a radiation, For example, a KrF excimer laser, an ArF excimer laser, an X ray, a soft X ray, or an electron beam is preferable, and EUV light or an electron beam is especially preferable.

  In the development step, an alkali developer is usually used. As the alkali developer in the development step, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used. In addition, inorganic alkalis (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, silica) Sodium, sodium metasilicate, etc., primary to tertiary amines (eg, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine), alcohol amines (eg, dimethylethanolamine, triethanolamine) Etc.), and alkaline aqueous solutions such as cyclic amines (for example, pyrrole, pihelidine, etc.) can also be used.

Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
As the rinsing liquid, pure water is preferable, and an appropriate amount of a surfactant can be added and used.

  In addition, before forming a photosensitive film | membrane, you may coat an antireflection film | membrane previously on a board | substrate. As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

<Polymerizable compound corresponding to repeating unit (A)>
(Synthesis Example 1: M-I-3)
100.00 parts by mass of p-acetoxystyrene was dissolved in 400 parts by mass of ethyl acetate, cooled to 0 ° C., 47.60 parts by mass of sodium methoxide (28% methanol solution) was added dropwise over 30 minutes, For 5 hours. Ethyl acetate was added and the organic layer was washed three times with distilled water and then dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 131.70 parts by mass of p-hydroxystyrene (54% ethyl acetate solution). It was.

  p-Hydroxystyrene (54% ethyl acetate solution) 18.52 parts by mass is dissolved in ethyl acetate 56.00 parts by mass to obtain 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl. 31.58 parts by mass of difluoride was added and cooled to 0 ° C. A solution prepared by dissolving 12.63 parts by mass of triethylamine in 25.00 parts by mass of ethyl acetate was added dropwise over 30 minutes, and the mixture was stirred at 0 ° C. for 4 hours. Ethyl acetate was added and the organic layer was washed 3 times with saturated brine, and then the solvent was distilled off. 35.00 g of the obtained compound was dissolved in 315 parts by mass of methanol, cooled to 0 ° C., 245 parts by mass of 1N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off, ethyl acetate was added, and the organic layer was washed 3 times with saturated brine, and then the solvent was distilled off to obtain 34.46 parts by mass of Compound A.

  42.86 parts by mass of p-toluenesulfonic acid (2-ethyl) hexyl was added to 25.80 parts by mass of 4-phenylpyridine N-oxide, and the mixture was stirred at 100 ° C. for 2 hours. The mixture was allowed to cool to room temperature, and the precipitated solid was filtered and washed with 100.00 parts by mass of ethyl acetate. The obtained white solid was dissolved in 30.00 parts by mass of methanol, and 35.55 parts by mass of Compound B was obtained from the obtained solution using an ion exchange resin (Amberlite®; IRA410).

30.00 parts by mass of Compound A was dissolved in 100.00 parts by mass of methanol, 21.95 parts by mass of Compound B was added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off, distilled water was added, and the mixture was extracted 3 times with chloroform. The obtained organic layer was washed with distilled water three times, and then the solvent was distilled off to obtain 45.86 parts by mass of the target compound (M-I-3).

¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 9.04 (d, 2H), 8.34 (d, 2H), 7.81 (d, 2H), 7.55 (m, 3H), 7.42 (d, 2H), 7.22 (d, 2H), 6.68 (dd, 1H), 5.74 (d, 1H), 5.32 (d, 1H), 4.57 (d, 2H), 1.58 (m, 15H).

  Hereinafter, similarly, polymerizable compounds (M-I-4, M-I-31, M-I-32, M-I-80, M-I-81, corresponding to other repeating units (A), M-I-96, M-I-97, M-I-109, M-I-111, M-II-44, M-II-45, M-II-81, M-II-82, M- III-5, M-III-7, M-III-49, M-III-85, M-III-86, M-III-106, M-III-108) were synthesized.

<Synthesis of Resin (P)>
(Synthesis Example 2: P-1)
9.33 parts by mass of methyl ethyl ketone was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, 6.54 parts by mass of the monomer (M-I-3) obtained in Synthesis Example 1 above, 6.70 parts by mass of monomer having the following structure, 6.76 parts by mass of 4-hydroxystyrene, A mixed solution of 37.33 parts by mass of methyl ethyl ketone and 1.51 parts by mass of dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] 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, reprecipitation is performed with a large amount of hexane / ethyl acetate, the obtained solid is dissolved again in acetone, reprecipitation is performed with a large amount of water / methanol, and vacuum drying is performed. 9.5 mass parts of resin (P-1) was obtained.

The weight average molecular weight (Mw: converted to polystyrene) obtained from GPC (carrier: N-methyl-2-pyrrolidone (NMP)) of the obtained resin was Mw = 9500, and the dispersity was Mw / Mn = 1.72. there were.

Thereafter, resins P-2 to P-26 were synthesized in the same manner. Table 3 below shows the composition ratio (mol%; corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

<Resist evaluation>
The components shown in Table 4 below are dissolved in a solvent, and a solution with a solid content of 4% by mass is prepared for each of the components. A radioactive resin composition was prepared. The actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in Table 4 below.
In addition, about each component in the following table, ratio when using two or more is a mass ratio. Moreover, the density | concentration of each component represents the mass concentration (mass%) with respect to the total solid.

(Exposure condition 1: EB exposure; Examples 1 to 28 and Comparative Examples 1 and 2)
The prepared radiation-sensitive resin composition was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, dried by heating on a hot plate at 120 ° C. for 90 seconds, and a film thickness of 100 nm. A radiation sensitive film was formed. This radiation sensitive 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 130 ° 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 spin-dried to obtain a resist pattern.

(Exposure condition 2: EUV exposure; Examples 29 to 34 and Comparative Example 3)
The prepared radiation-sensitive resin composition was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, dried by heating on a hot plate at 120 ° C. for 90 seconds, and a film thickness of 100 nm. A radiation sensitive film was formed. This radiation sensitive film was irradiated with an EUV exposure apparatus, and immediately after the irradiation, it was heated on a hot plate at 130 ° 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 spin-dried to obtain a resist pattern.

(Sensitivity evaluation)
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 evaluation)
The resolving power was defined as the limiting resolving power (minimum width at which lines and spaces were separated and resolved) at the irradiation amount showing the above sensitivity.

(Pattern shape evaluation)
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-stage evaluation of a rectangle, a T-top, and a taper was performed. .

(LER evaluation)
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.

  The abbreviations shown in the table are as follows.

[Photoacid generator]

[Basic compounds]
TBAH: Tetrabutylammonium hydroxide TOA: Tri (n-octyl) amine TPI: Triphenylimidazole [Surfactant]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)
W-4: PF6320 (manufactured by OMNOVA) (fluorine-based)
〔solvent〕
S1: Propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane)
S2: Propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol)
S3: Ethyl lactate.

From the results described in the above table, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention simultaneously exhibits high sensitivity, high resolution, good pattern shape, and good line edge roughness in EB exposure. It is clear that we are satisfied.
Moreover, 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 exposure.

Claims (10)

  It includes a repeating unit (A) that decomposes upon irradiation with actinic rays or radiation to generate an acid, and the repeating unit (A) has a cationic structure including a monocyclic or polycyclic nitrogen-containing heterocycle. A positive-type actinic ray-sensitive or radiation-sensitive resin composition containing the resin (P).   The composition of claim 1, wherein the cationic structure comprises an azinium cation. The composition according to claim 1, wherein the cationic structure is represented by the following general formula (AZ).

In the formula, R represents a monovalent substituent.

Represents a monocyclic or polycyclic nitrogen-containing heterocycle.
S ^N represents a substituent. m represents an integer of 0 or more.   The composition according to any one of claims 1 to 3, wherein the resin (P) further includes a repeating unit (B) that decomposes by the action of an acid to generate an alkali-soluble group. The composition according to any one of claims 1 to 4, wherein the resin (P) further contains a repeating unit represented by the following general formula (IV).

In the formula, R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to Ar ₄ to form a ring, and R ₄₂ in this case represents an alkylene group.
X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or an alkylene group.
Ar ₄ represents a divalent aromatic ring group.
n represents an integer of 1 to 4.   The composition according to any one of claims 1 to 5, wherein the repeating unit (A) has a structure that generates an acid group in a side chain of the resin (P) by irradiation with the actinic ray or radiation. object.   The composition according to any one of claims 1 to 6, which is exposed to an electron beam, an X-ray or a soft X-ray.   A resist film formed using the composition according to claim 1. Forming a film using the composition according to any one of claims 1 to 7,
Exposing the film;
Developing a pattern of the exposed film.   The method according to claim 9, wherein the exposure is performed by an electron beam, an X-ray, or a soft X-ray.