JP2012255845A - Actinic ray sensitive or radiation sensitive resin composition, and actinic ray sensitive or radiation sensitive film and method for forming pattern using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic ray sensitive or radiation sensitive resin composition which is high in sensitivity and excellent in LER, exposure latitude and pattern shape, and to provide an actinic ray sensitive or radiation sensitive film and a method for forming a pattern using the same.SOLUTION: There is provided an actinic ray sensitive or radiation sensitive resin composition containing a resin including: a repeating unit (A) having an ionic structural moiety that is decomposed by irradiation with actinic rays or radiation to generate an acid anion at a side chain of the resin; a repeating unit (B) represented by the following general formula (B1); and a repeating unit (C) that is decomposed by action of an acid to generate an alkali soluble group (in the formula (B1), Rrepresents a hydrogen atom, an alkyl group, a halogen atom or a cyano group, Y represents a single bond or a divalent linking group, Z represents a single bond or a divalent linking group, Ar represents an aromatic ring group and p represents an integer of 1 or more.).

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a lithography process performed in a manufacturing process such as a VLSI, a high-capacity microchip, an imprint mold structure, and other photofabrication processes. The present invention relates to an actinic ray-sensitive or radiation-sensitive film and a pattern forming method using the same. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition for electron beam, X-ray or EUV light preferably applied to the above process, and actinic ray-sensitive or radiation-sensitive property using the same. The present invention relates to a film and a pattern forming method.

  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 being developed. (See, for example, Patent Documents 1 and 2).

  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 3 and 4, And non-patent document 1).

  In particular, EUV lithography is positioned as a next-generation or next-generation pattern forming technique, and a resist having high sensitivity and high resolution is desired. In particular, high sensitivity is a very important issue for shortening the wafer processing time. However, in EUV resist, if high sensitivity is to be pursued, not only the resolution is lowered but also the line edge roughness (LER). ) Worsening occurs. Therefore, development of a resist that satisfies these characteristics at the same time is strongly desired.

  Here, the line edge roughness means that the resist pattern and the edge of the substrate interface irregularly fluctuate in the direction perpendicular to the line direction due to the characteristics of the resist. Say that the edge looks uneven. When the unevenness is transferred to the processed substrate by an etching process using a resist as a mask, there arises a problem that the electrical characteristics of the device deteriorate and the yield decreases. In particular, in the ultrafine region of 0.10 μm or less, the line edge roughness is an extremely important improvement issue. There is a trade-off between high sensitivity and good line edge roughness, and it is very important how to satisfy these simultaneously.

  Further, in EUV lithography, it is known that out-of-band light (ultraviolet rays other than the wavelength of EUV) is generated from an exposure source, and the exposure latitude and pattern shape are deteriorated (for example, Non-Patent Document 2 and 3). Therefore, it is desired to develop a resist that satisfies not only high sensitivity and good line edge roughness, but also good exposure latitude and pattern shape.

JP 2009-86358 A JP 2010-237662 A JP 2004-158287 A JP 2008-162101 A

Yoshihiko Hirai, “Nanoimprint Basics and Technology Development / Application Deployment-Nanoimprint Substrate Technology and Latest Technology Deployment”, Frontier Publishing, June 2006 Proc. of SPIE Vol. 7273, 72731W, 2009 Proc. of SPIE Vol. 7636, 763626, 2010

  In view of the above background art, the present invention has high sensitivity, good LER, good exposure latitude, and good pattern shape, particularly in lithography using EUV light as an exposure light source. It is an object of the present invention to provide an actinic ray-sensitive or radiation-sensitive resin composition that satisfies the above requirements, an actinic ray-sensitive or radiation-sensitive film and a pattern forming method using the same.

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

[1] A repeating unit (A) having an ionic structure site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin;
A repeating unit (B) represented by the following general formula (B1);
An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having a repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group:

In general formula (B1),
R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, or a cyano group;
Y represents a single bond or a divalent linking group;
Z represents a single bond or a divalent linking group;
Ar represents an aromatic ring group;
p represents an integer of 1 or more.

[2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit (B) is a repeating unit represented by the following general formula (B2):

In general formula (B2),
R ₃ represents a hydrogen atom or an alkyl group.

[3] The actinic ray-sensitive composition according to [1], wherein the repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group is a repeating unit represented by the following general formula (C1): Radiation sensitive resin composition:

In general formula (C1),
R ₅₃ represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group;
R ₅₄ represents a hydrogen atom;
R ₅₅ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group or an aromatic ring group;
R ₅₆ represents an aromatic ring group;
R ₅₅ and R ₅₆ may combine with each other to form a ring.

[4] The actinic ray-sensitive or radiation-sensitive material according to any one of [1] to [3], wherein the resin (P) further has a repeating unit (D) represented by the following general formula (D3). Resin composition.

In general formula (D3),
R ₄₃ represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group;
X ₁ represents a single bond or a divalent linking group;
Ar ₄ represents an (n + 1) -valent aromatic ring group;
n represents an integer of 1 to 4.

[5] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4].

[6] Forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], exposing the film to EUV light, and exposing A pattern forming method comprising developing a film.

  According to the present invention, particularly in lithography using EUV light as an exposure light source, high sensitivity, good LER, good exposure latitude, and good pattern shape are satisfied at the same time. An actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film using the same, and a pattern forming method can be provided.

  Hereinafter, the present invention will be described in detail.

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

  As used herein, “active light” or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, soft X-rays, electron beams, etc. means. In the present invention, light means actinic rays or radiation.

  In addition, the term “exposure” in the present specification is not limited to exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in exposure.

  The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is, for example, a positive composition, typically a positive resist composition. Hereinafter, the structure of this composition is demonstrated.

[1] Resin (P)
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a resin (P). Resin (P) is composed of a repeating unit (A) having an ionic structure site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin, a repeating unit (B), and the action of an acid. And a repeating unit (C) that decomposes to generate an alkali-soluble group. Hereinafter, each repeating unit will be described.

[Repeating unit (B)]
The repeating unit (B) contained in the resin (P) is represented by the following general formula (B1).

In general formula (B1),
R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, or a cyano group;
Y represents a single bond or a divalent linking group;
Z represents a single bond or a divalent linking group;
Ar represents an aromatic ring group;
p represents an integer of 1 or more.

The alkyl group as R ₃ may be either linear or branched, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl. Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, i-butyl group, and may further have a substituent. Preferred examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, and a nitro group. Among them, examples of the alkyl group having a substituent include a CF ₃ group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, and hydroxymethyl. Group, alkoxymethyl group and the like are preferable.

  In addition, in this specification, in the case of the group name display which does not describe substitution and non-substitution, it treats as what does not exclude what has a substituent.

Examples of the halogen atom as R ₃ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

Y represents a single bond or a divalent linking group, and examples of the divalent linking group include an ether group (oxygen atom), a thioether group (sulfur atom), an alkylene group, an arylene group, a carbonyl group, a sulfide group, Sulfone group, —COO—, —CONH—, —SO ₂ NH—, —CF ₂ —, —CF ₂ CF ₂ —, —OCF ₂ O—, —CF ₂ OCF ₂ —, —SS—, —CH ₂ SO ₂ CH ₂ —, —CH ₂ COCH ₂ —, —COCF ₂ CO—, —COCO—, —OCOO—, —OSO ₂ O—, amino group (nitrogen atom), acyl group, alkylsulfonyl group, —CH═CH And —C—C≡C—, an aminocarbonylamino group, an aminosulfonylamino group, or a combination thereof. Y preferably has 15 or less carbon atoms, more preferably 10 or less carbon atoms.

  Y is preferably a single bond, an ether group, a thioether group or an amino group, more preferably an ether group or an amino group, and particularly preferably an ether group.

Z represents a single bond or a divalent linking group, and examples of the divalent linking group include an ether group (oxygen atom), a thioether group (sulfur atom), an alkylene group, an arylene group, a carbonyl group, a sulfide group, Sulfone group, —COO—, —CONH—, —SO ₂ NH—, amino group (nitrogen atom), acyl group, alkylsulfonyl group, —CH═CH—, aminocarbonylamino group, aminosulfonylamino group, or these Examples include groups consisting of combinations.

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

  Ar represents an aromatic ring group, specifically, phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, quinolinyl group, furanyl group, thiophenyl group, fluorenyl-9-one-yl group, anthraquinonyl group, phenanthralkyl. A nonyl group, a pyrrole group, etc. are mentioned, A phenyl group is preferable. These aromatic ring groups may further have a substituent. Preferred examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, and a sulfonylamino group. Group, aryl group such as phenyl group, aryloxy group, arylcarbonyl group, heterocyclic residue, etc. Among them, phenyl group suppresses deterioration of exposure latitude and pattern shape caused by out-of-band light It is preferable from the viewpoint.

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

The repeating unit (B) is more preferably a repeating unit represented by the following formula (B2).

In General Formula (B2), R ₃ represents a hydrogen atom or an alkyl group. The thing preferable as an alkyl group as R < ₃ > is the same as that of general formula (B1).

Specific examples of the repeating unit represented by formula (B1) or formula (B2) are shown below, but are not limited thereto.

  The content of the repeating unit (B) in the resin (P) of the present invention is preferably in the range of 1 to 50 mol% and more preferably in the range of 3 to 30 mol% with respect to all the repeating units of the resin (P). The range of 5 to 15 mol% is particularly preferable.

  Since the resin (P) of the present invention has the repeating unit (B), the exposure latitude, the pattern shape (remaining film amount) and the line edge roughness are good, and a highly sensitive pattern can be obtained. As the repeating unit (B) has a plurality of aromatic rings in one unit, it efficiently absorbs out-of-band light particularly when performing EUV exposure, and as a result, suppresses deterioration of pattern formability. It is thought that.

[Repeating unit (A)]
The repeating unit (A) is a repeating unit having an ionic structure site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin.

More specifically, the repeating unit (A) is preferably a repeating unit represented by any one of the following general formulas (I) to (III).

In the general formula (I), R ₁₃ represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group. X ₁₁ is, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), - CONH- or a divalent nitrogen Represents a non-aromatic heterocyclic group. L ₁₁ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a group obtained by combining two or more thereof. X ₁₂ is a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —OSO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), —CONH— or a divalent nitrogen-containing non-aromatic heterocyclic group is represented. Ar ₁ represents a divalent aromatic ring group. X ₁₃ represents a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —OSO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), Represents a divalent nitrogen-containing non-aromatic heterocyclic group. L ₁₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a divalent aromatic ring group. Z ₁ represents a site that becomes a sulfonic acid group when irradiated with actinic rays or radiation.

In the general formula (II), R ₂₃ represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group. Ar ₂ represents a divalent aromatic ring group. X ₂₁ represents —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —OSO ₂ —, —NR— (where R is a hydrogen atom or an alkyl group) or a divalent group. Represents a nitrogen-containing non-aromatic heterocyclic group. L ₂₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. X ₂₂ is a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —OSO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), Represents a divalent nitrogen-containing non-aromatic heterocyclic group.

L ₂₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a divalent aromatic ring group. Z ₂ represents a site that becomes a sulfonic acid group upon irradiation with actinic rays or radiation.

In the general formula (III), R ₃₃ represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group. X ₃₁ represents a single bond, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), - CONH- or 2 Represents a valent nitrogen-containing non-aromatic heterocyclic group. L ₃₁ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. X ₃₂ is a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —OSO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), Represents a divalent nitrogen-containing non-aromatic heterocyclic group. L ₃₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a divalent aromatic ring group. Z ₃ represents a group that becomes an imido acid group or a methido acid group upon irradiation with actinic rays or radiation.

In the general formulas (I) to (III), R ₁₃ , R ₂₃ , and R ₃₃ each represent a hydrogen atom, an alkyl group, a halogen atom, or a cyano group, and the alkyl group has 1 to 4 carbon atoms. Particularly preferred are those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, t-butyl group, chloromethyl group, trifluoromethyl group and hydroxymethyl group. Atoms are preferred. Particularly preferred groups as R ₁₃ , R ₂₃ and R ₃₃ are a hydrogen atom or a methyl group.

X _11, X ₃₁ is, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), - CONH- or 2 Represents a valent nitrogen-containing non-aromatic heterocyclic group (X ₃₁ may be a single bond), and examples of the —NR— alkyl group include a methyl group, an ethyl group, an n-propyl group, and a t-butyl group. Examples of the divalent nitrogen-containing non-aromatic heterocyclic group include a divalent linking group having the following structure.

X ₁₁ is preferably —O—, —CO—, —COO—, —NR— or —CONH—, particularly preferably —COO— or —CONH—. X ₃₁ is preferably a single bond in addition to the preferred example of X ₁₁ .

L ₁₁ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group or a group obtained by combining two or more of these, and the alkylene group is, for example, a methylene group, an ethylene group, a propylene group, or a butylene group. Such an alkylene group having 1 to 4 carbon atoms is preferred, and examples of the alkenylene group include a group having a double bond at an arbitrary position of the alkylene group, and the divalent aliphatic hydrocarbon ring group includes, for example, Preferred examples include a divalent aliphatic hydrocarbon ring group such as a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, and a diamantannylene group. Examples of the group obtained by combining two or more of these include -alkylene group-O-alkylene group-, -alkylene group-OCO-alkylene group-, -valent aliphatic hydrocarbon ring group-O-alkylene group-, -Alkylene group-CONH-alkylene group- and the like.

X ₁₂ represents a single bond, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - OSO 2 -, - NR -, - CONH- or a divalent nitrogen containing Represents a non-aromatic heterocyclic group, preferably a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —OSO ₂ —, more preferably a single bond, — S -, - OCO -, - OSO 2 - is particularly preferred.

Ar ₁ and Ar ₂ represent a divalent aromatic ring group. For example, arylene groups such as phenylene group, tolylene group and naphthylene group, aralkylene group, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, and triazine , Imidazole, benzimidazole, triazole, thiadiazole, thiazole, and the like, and a phenylene group, a naphthylene group, a biphenylene group, and a phenylene group substituted with a phenyl group are preferable. Further, the divalent aromatic ring group may be a group in which a divalent aromatic ring group and an alkylene group are combined. In this case, the alkylene group is preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, or a butylene group. In particular, a group in which a phenylene group and an ethylene group are combined or a group in which a phenylene group and a methylene group are combined is preferable.

X ₁₃ represents a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —OSO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), represents a divalent nitrogen-containing non-aromatic heterocyclic group, -O -, - CO -, - COO -, - OCO -, - SO 2 -, - OSO 2 - are more preferable, -OSO ₂ - is particularly preferable.

L ₁₂ , L ₂₂ and L ₃₂ represent an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a divalent aromatic ring group, and these groups have a part or all of hydrogen atoms, It is preferably substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, or a cyano group, and part or all of the hydrogen atoms are fluorine atoms or fluorinated alkyl groups (more preferably perfluoro An alkylene group and a divalent aromatic ring group substituted with an alkyl group are more preferable, and an alkylene group and a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms are substituted with a fluorine atom are particularly preferable.

The alkylene group in L ₁₂ , L ₂₂ and L ₃₂ is more preferably an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group or a hexylene group, and an alkylene group having 1 to 4 carbon atoms. The group is particularly preferred. The alkenylene group includes a group having a double bond at an arbitrary position of the alkylene group. Examples of the divalent aliphatic hydrocarbon ring group include a divalent aliphatic hydrocarbon ring group having 3 to 17 carbon atoms such as a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, and a diamantannylene group. Is a preferred example. Examples of the divalent aromatic ring group include an arylene group such as a phenylene group, a tolylene group, and a naphthylene group, and a group in which a divalent aromatic ring group and an alkylene group are combined.

The preferred specific examples of L ₁₂ , L ₂₂ and L ₃₂ are shown below.

X ₂₁ is —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —OSO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group), divalent Represents a nitrogen-containing non-aromatic heterocyclic group, more preferably —O—, —S—, —CO—, —OCO—, —SO ₂ —, —OSO ₂ —, —O—, —OCO—, — OSO ₂ -is particularly preferred.

L ₂₁ and L ₃₁ are a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group in which two or more of these are combined (for example, an -alkylene group -2 value) Aromatic ring group-, -2 valent aliphatic hydrocarbon ring group-alkylene group-, etc.), or -OCO-, -COO-, -O-, -CONH- or -S- as a linking group. And a combination of two or more of these (for example, -alkylene group-OCO-2 valent aromatic ring group-, -alkylene group-S-2 valent aromatic ring group-, -alkylene group-O-alkylene group-2). Valent aromatic ring group-etc.).

As the alkylene group, alkenylene group, and divalent aliphatic hydrocarbon ring group, the alkylene group, alkenylene group, and divalent aliphatic hydrocarbon ring group in L ₁₁ in the general formula (I) are described above. The same specific example is given. As an aromatic ring group, for example, an arylene group such as a phenylene group, a tolylene group, a naphthylene group, or a thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, Heterocycles such as thiazole can be mentioned. The divalent aromatic ring group may be a group in which a divalent aromatic ring group and an alkylene group are combined. In this case, the alkylene group is preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, or a butylene group. In particular, a group in which a phenylene group and an ethylene group are combined or a group in which a phenylene group and a methylene group are combined is preferable.

X ₂₂ and X ₃₂ are each a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —OSO ₂ —, —NR— (where R is a hydrogen atom or alkyl Group), which represents a divalent nitrogen-containing non-aromatic heterocyclic group, —O—, —S—, —CO—, —OCO—, —SO ₂ —, —OSO ₂ — is more preferred, —O— , —OCO— and —OSO ₂ — are particularly preferable.

Z ₁ and Z ₂ in the above formulas (I) and (II) each represent a site that becomes a sulfonic acid group upon irradiation with actinic rays or radiation, and Z _{3 in the} above formula (III) represents actinic rays or radiation. It represents a site that becomes an imido acid group or a methido acid group by irradiation. Z ₁ , Z ₂ and Z ₃ are all preferably onium salts, more preferably sulfonium salts or iodonium salts. In the case of the above formulas (I) and (II), the following general formula (ZI) or (ZII) The structure represented by is particularly preferable.

In the above general formula (ZI) and general formula (ZII), R ₂₀₁ , R ₂₀₂ , R ₂₀₃ , R ₂₀₄ , and R ₂₀₅ each independently represents an organic group.

Two or more of the _{R 201, R 202} and _{R 203,} or _{R 204} and _{R 205} may form a ring structure, such as an alkylene group bonded to.

The organic group represented by R ₂₀₁ or R ₂₀₄ is particularly preferably an aryl group. In this case, the onium salt represented by the general formula (ZI) or the general formula (ZII) is an arylsulfonium salt or an aryliodonium salt. It becomes. These aryl groups may be an aromatic ring such as a phenyl group or a naphthyl group or a heterocyclic ring containing a hetero atom, and more preferably a phenyl group.

  Examples of the arylsulfonium salt include groups corresponding to triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, aryldicycloalkylsulfonium.

In the general formula (ZI), when two or more of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are an aryl group, the other group may be an alkyl group or a monovalent aliphatic hydrocarbon ring group. Examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group and monovalent aliphatic hydrocarbon ring group in R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent, preferably an alkyl group having 1 to 4 carbon atoms, 1 to 1 carbon atoms. 4 is an alkoxy group. In the case of substitution of an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

When R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI) are all groups representing an organic group having no aromatic ring, R _{201 to} R ₂₀₃ are preferably each independently an alkyl group. A monovalent aliphatic hydrocarbon ring group, an allyl group and a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxoaliphatic hydrocarbon ring group, an alkoxycarbonylmethyl group, Particularly preferred is a 2-oxoaliphatic hydrocarbon ring group.

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

One embodiment of the group represented by (ZI) is a structure represented by the following general formula (ZI-1A).

In General Formula (ZI-1A), R ^{1a to} R ^13a each independently represent a hydrogen atom or a substituent, and at least one of R ^{1a to} R ^13a may be a substituent containing an alcoholic hydroxyl group. preferable. Za is a single bond or a divalent linking group.

  Za represents a single bond or a divalent linking group, preferably a single bond or a substituent having no electron withdrawing property, more preferably a single bond, an ether group or a thioether group, particularly preferably. It is a single bond.

When R < ^1a > -R <^13a> is a substituent containing an alcoholic hydroxyl group, R < ^1a > -R <^13a> is represented by -W-OH, and W in a formula represents a single bond or a bivalent coupling group. Preferred W is a single bond, an alkylene group, —O—, —SO ₂ —, or —CONH—. A representative substituent containing an alcoholic hydroxyl group is —CH ₂ CH ₂ OH.

The number of alcoholic hydroxyl groups in the general formula (ZI-1A) is preferably 1 to 6, and more preferably 1 to 3. The position of the group containing an alcoholic hydroxyl group in the general formula (ZI-1A) is preferably R ^{9a to} R ^13a .

When R ^{1a to} R ^13a are not a group containing an alcoholic hydroxyl group, these groups are preferably a hydrogen atom, an alkyl group (including a monovalent aliphatic hydrocarbon ring group), a halogen atom, an alkoxy group, an aryl group, A cyano group, a carboxyl group, an aryloxy group, an acylamino group, an alkylthio group, an alkoxycarbonyl group, or a nitro group.

Another example of the group represented by (ZI) is a group having a phenacylsulfonium salt structure represented by the following general formula (ZI-3).

In general formula (ZI-3), R _x and R _y each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an allyl group, or a vinyl group. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group or a monovalent aliphatic hydrocarbon ring group. R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an alkoxy group or a halogen atom.

Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure. Examples of the group to be formed include a butylene group and a pentylene group.

In R _{1c to} R _7c , the alkyl group can include, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and a monovalent aliphatic hydrocarbon Examples of the cyclic group include monovalent aliphatic hydrocarbon cyclic groups having 3 to 8 carbon atoms, and examples of the alkoxy group include linear or branched alkoxy groups having 1 to 5 carbon atoms and 3 to 8 carbon atoms. The cyclic alkoxy group can be mentioned.

Among the above, preferably, the sum of the carbon numbers of R _{1c to} R _5c is 2 to 15, thereby improving the solvent solubility of the resin (P) and suppressing the generation of particles during storage. .

Examples of the alkyl group and monovalent aliphatic hydrocarbon ring group in R _x and R _y include the same alkyl group and monovalent aliphatic hydrocarbon ring group as in R _{1c to} R _7c , and 2- An oxoalkyl group, a 2-oxoaliphatic hydrocarbon ring group, and an alkoxycarbonylmethyl group are more preferable.

R _x and R _y are preferably an alkyl group having 4 or more carbon atoms or a monovalent aliphatic hydrocarbon ring group, more preferably an alkyl group having 6 or more carbon atoms, more preferably 8 or more carbon atoms, or a monovalent group. An aliphatic hydrocarbon ring group.

Next, in the case of the general formula (ZII), in the general formula (ZII), R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group, or a monovalent aliphatic hydrocarbon ring group. Specific examples of the group, alkyl group, and monovalent aliphatic hydrocarbon ring group are the same as the aryl group, alkyl group, and monovalent aliphatic hydrocarbon ring group mentioned in the above (ZI-1) group. Can be mentioned.

Next, Z ₃ in the general formula (III) represents an onium salt that becomes an imido acid group or a methido acid group upon irradiation with actinic rays or radiation, and examples of the onium salt represented by Z ₃ include a sulfonium salt or iodonium. A salt is preferable, and a structure represented by the following general formula (ZIII) or (ZIV) is preferable.

In general formulas (ZIII) and (ZIV), Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ each independently represent —CO— or —SO ₂ —, and more preferably —SO ₂ —. It is.

Rz ₁ , Rz ₂ and Rz ₃ each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group. An embodiment in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluoroalkyl group (more preferably a perfluoroalkyl group) is more preferred, and an embodiment in which 30 to 100% of the number of hydrogen atoms is substituted with a fluorine atom is particularly preferred. . The alkyl group is more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. As the monovalent aliphatic hydrocarbon ring group, a monovalent aliphatic hydrocarbon ring group having 3 to 6 carbon atoms is more preferable. As the aryl group, an aryl group having 6 to 10 carbon atoms is more preferable, and a phenyl group is particularly preferable. As the aralkyl group, an aralkyl group in which an alkylene group having 1 to 4 carbon atoms and the aryl group are bonded is particularly preferable.

A ⁺ represents a sulfonium cation or an iodonium cation, and preferred examples include the sulfonium cation in the general formula (ZI) and the iodonium cation structure in the general formula (ZII).

Examples of the polymerizable monomer unit corresponding to the repeating unit of the general formula (I) include sulfonic acid units generated by detachment of cations by irradiation with actinic rays or radiation.

Next, the polymerizable monomer unit corresponding to the repeating unit of the general formula (II) is exemplified below as a sulfonic acid unit generated by detachment of a cation by irradiation with actinic rays or radiation.

Next, examples of the polymerizable monomer unit corresponding to the repeating unit of the general formula (III) include imide acid and methide acid units generated by cation detachment upon irradiation with actinic rays or radiation.

  The polymerizable compound corresponding to the repeating units of the general formulas (I) to (III) is, for example, by selectively reacting one sulfonyl halide part of a bissulfonyl halide compound with an amine, alcohol, etc., to form a sulfonamide bond, sulfone After forming an acid ester bond, it can be obtained by a method of hydrolyzing the other sulfonyl halide moiety or a method of opening a cyclic sulfonic anhydride with an amine or alcohol. Also, US Pat. Fluorine Chem. 105 (2000) 129-136; Fluorine Chem. 116 (2002) 45-48 can also be easily synthesized.

Specific examples of the cation of the onium salt represented by Z _{1 to} Z ₃ in the general formulas (I) to (III) are shown below.

In Table 1 below, specific examples of the polymerizable compound (M) corresponding to the repeating units of the general formulas (I) to (III) are shown as cation structures ((Z-1) to (Z-58) exemplified above). ) And an anion structure (the hydrogen atom of the organic acid in (I-1) to (I-16), (II-1) to (II-21), (III-1) to (III-16) exemplified above) It is shown as a combination of anions excluding.

  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% with respect to all the repeating units of the resin (P). More preferably, it is the range of 3-40 mol%.

  Since the resin (P) of the present invention has a repeating unit (A) having an ionic structure site that generates an acid anion in the side chain as described above, the exposure latitude and resolution are particularly excellent. . This is presumably because the acid is prevented from diffusing too much.

[Repeating unit (C)]
The repeating unit (C) is a repeating unit that is decomposed by the action of an acid to generate an alkali-soluble group (hereinafter sometimes referred to as “a repeating unit having an acid-decomposable group”).

A preferred group as the acid-decomposable group is a group obtained by substituting an alkali-soluble hydrogen atom with a group capable of leaving by an acid. Examples of the group having an alkali-soluble hydrogen atom include a phenolic hydroxyl group, a carboxyl group, and a fluorinated alcohol group. A sulfonic acid group and a sulfonamide group are preferable, and a phenolic hydroxyl group, a carboxyl group, and a fluorinated alcohol group (preferably hexafluoroisopropanol) are particularly preferable. Examples of a group released by an acid, _{e.g., -C (R 36) (R} 37) (R 38), - C (R 01) (R 02) (OR 39), - C (= O) - _{O-C (R 36) (} R 37) (R 38), - 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 above formula, R _{36 to} R ₃₉ are each independently an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, an alkylene group. Represents a group or alkenyl group in which a group and a monovalent aromatic ring group are combined, and R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, or a monovalent aromatic ring group. And represents a group or alkenyl group in which an alkylene group and a monovalent aromatic ring group are combined, and Ar represents a monovalent aromatic ring group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

As the repeating unit (C), a repeating unit represented by the following general formula (C1) is more preferable.

In the general formula (C1), R ₅₃ represents a hydrogen atom, an alkyl group, a halogen atom, or a cyano group, R ₅₄ represents a hydrogen atom, R ₅₅ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group. Or represents an aromatic ring group, and R ₅₆ represents an aromatic ring group. R ₅₅ and R ₅₆ may combine with each other to form a ring.

  General formula (C1) will be described in more detail.

First, R ₅₃ will be described below. As the alkyl group, preferably an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a hexyl group, a trifluoromethyl group, a hydroxymethyl group, A substituted alkyl group such as a chloromethyl group is exemplified, and an alkyl group having 1 to 3 carbon atoms is more preferred. The monovalent aliphatic hydrocarbon ring group is preferably a monovalent monovalent aliphatic hydrocarbon ring group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. As the halogen atom, a fluorine atom is particularly preferable. As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R ₅₃ are preferable.

Next, R ₅₅ will be described below. Preferred examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The aliphatic hydrocarbon ring group is preferably a monocyclic ring such as a cyclopentyl group or a cyclohexyl group, or a polycyclic group such as a norbornyl group, an adamantyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group having 3 to 3 carbon atoms. 20 aliphatic hydrocarbon ring groups are exemplified, and examples of the aromatic ring group include a phenyl group and a naphthyl group.

As the aromatic ring group represented by R ₅₆ , those having 6 to 20 carbon atoms such as phenyl group, naphthyl group, anthryl group, or fluorene group are preferable, and those having 6 to 15 carbon atoms are more preferable.

Specific examples of the repeating unit represented by the general formula (C1) are shown below.

Especially, the repeating unit shown below is more preferable.

  The content of the repeating unit (C) in the resin (P) of the present invention is preferably in the range of 5 to 80 mol%, particularly in the range of 7 to 70 mol%, based on all the repeating units of the resin (P). preferable. The ratio of the repeating unit (A) to the repeating unit (C) in the resin (number of moles of A / number of moles of B) is preferably 0.04 to 1.0, and preferably 0.05 to 0.9. More preferred is 0.06 to 0.8.

[Repeating unit (D)]
It is preferable that the resin (P) of the present invention further has a repeating unit (D) having an aromatic ring group, which is different from the repeating unit (A) and the repeating unit (C). When the resin (P) has the repeating unit (D), the out-band light can be absorbed more efficiently, and the pattern formability is further improved. As a repeating unit (D), the repeating unit represented by the following general formula (D1) can be mentioned, for example.

In formula (D1), R ₄₃ represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group, and Q represents a group containing an aromatic ring group. .

Specific examples of R ₄₃ are more preferably a hydrogen atom, an alkyl group, a halogen atom, or a cyano group, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (—CH ₂ —). OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom are particularly preferable.

  In the general formula (D1), Q is an aromatic group such as a phenyl group, a naphthyl group, an anthranyl group, or a phenanthryl group, and more preferably a phenyl group.

As the repeating unit represented by the general formula (D1), a repeating unit represented by the following general formula (D3) is more preferable.

In the formula (D3), R ₄₃ is the same as in the general formula (D1), X ₁ represents a single bond or a divalent linking group, Ar ₄ represents an (n + 1) valent aromatic ring group, and n represents The integer of 1-4 is represented.

X ₁ is preferably a single bond, —COO—, —CONH—, —OCO—, —CO—, —S—, —SO—, —SO ₂ —, or a group in which these and an alkylene group are linked. , —COO—, —CONH—, —SO ₂ — or —SO ₃ — is more preferable.

Ar ₄ is, when n is 1, 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, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole , Triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like, and divalent aromatic ring groups including a heterocycle can be exemplified, and a phenylene group, a naphthylene group, and a biphenylene group are particularly preferable. When n is 2 to 4 or more, a trivalent to pentavalent aromatic ring group corresponding to the divalent aromatic ring group mentioned above is preferable.

Specific examples of the repeating unit (D) contained in the resin (P) are shown below. In the formula, a represents an integer of 0 to 2.

  The content of the repeating unit (D) in the resin (P) is preferably in the range of 5 to 90 mol%, more preferably in the range of 10 to 80 mol% with respect to all the repeating units of the resin (P). More preferably, it is the range of 20-70 mol%. The repeating unit (D) contained in the resin (P) may contain a combination of two or more types.

  In the present invention, the content (mol%) of the repeating unit (D) in the resin (P) is preferably equal to or higher than the content of the repeating unit (C).

[Repeating unit (E)]
The resin (P) preferably further has a repeating unit (E) having a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer, and as such a group, a lactone structure, Examples thereof include a phenyl ester structure.

As the repeating unit (E), a repeating unit represented by the following general formula (E1) is more preferable.

In general formula (E1), V represents a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer, Ab represents a single bond or a divalent linking group, and Rb ₀ represents , A hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 4 carbon atoms).

  V is preferably a group having an ester bond, and more preferably a group having a lactone structure.

The group having a lactone structure is preferably a 5- to 7-membered ring lactone structure, and the 5- to 7-membered ring lactone structure is condensed with another ring structure in the form of forming a bicyclo structure or a spiro structure. preferable. It is more preferable to have a lactone structure represented by any one 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 represented by (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17). Lactone structure.

In the above structure, Rb ₂ is a substituent, and n ₂ represents an integer of 0 to 4. Preferred Rb ₂ is an alkyl group having 1 to 4 carbon atoms, a cyano group, an alkoxycarbonyl group, a carboxyl group, or an acid-decomposable group.

  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.

Examples of Ab include a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic aliphatic hydrocarbon ring structure, an ether group, an ester group, a carbonyl group, or a divalent linking that combines these groups. A group, preferably a single bond or a divalent linking group represented by -Ab ₁ -CO _2- . Here, Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic aliphatic hydrocarbon ring group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. It is.

Specific examples of the repeating unit (E) are shown below. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The content of the repeating unit (E) in the resin (P) is preferably in the range of 0.5 to 80 mol%, more preferably 1 to 60 mol based on all repeating units of the resin (P). %, More preferably in the range of 2 to 40 mol%. Two or more repeating units (E) may be used in combination.

  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 conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.

  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.

  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. 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.

  For the purpose of improving the performance of the resin according to the present invention, the resin (P) may further contain a repeating unit derived from another polymerizable monomer as long as the dry etching resistance is not significantly impaired. Examples of other polymerizable monomers that can be used include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and crotonic acid esters. It is a compound having one addition polymerizable unsaturated bond.

  The content of the resin (P) of the present invention is preferably 30 to 99.99% by mass, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and preferably 50 to 99. 97 mass% is more preferable, and 70-99.95 mass% is especially preferable.

  Preferred specific examples of the resin (P) include, for example, one or more repeating units (A) selected from the specific examples of the repeating units represented by the general formulas (I) to (III) / the general formula ( One or more repeating units (B) selected from the specific examples of the repeating units represented by B1) / one or more repeating units selected from the specific examples of the repeating units represented by the general formula (C1) Resin having (C), represented by one or more repeating units (A) selected from specific examples of repeating units represented by the general formulas (I) to (III) / represented by the general formula (B1) One or more repeating units (B) selected from specific examples of repeating units / one or more repeating units (C) selected from specific examples of repeating units represented by the general formula (C1) / general The repeating unit represented by the formula (D3) 1 or more repeating units selected from the specific examples (D) can be exemplified resins having.

Although the more preferable specific example of resin (P) is shown below, this invention is not limited to these.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further include a basic compound, a resin that decomposes by the action of an acid to increase the dissolution rate in an aqueous alkaline solution, and a conventional photoacid generator. Agents, surfactants, acid-decomposable dissolution inhibiting compounds, dyes, plasticizers, photosensitizers, compounds that promote dissolution in developers, and / or compounds having proton acceptor functional groups, and the like. .

[2] Basic compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a nitrogen-containing organic basic compound as a basic compound.

  As the usable basic compound, for example, compounds classified into the following (1) to (4) are preferably used.

(1) Secondary or tertiary amino compounds Specific examples of these compounds include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, and dicyclohexyl. Methylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexylaniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline, triethanolamine, N, N-dihydroxyethylaniline, tris (methoxyethoxyethyl) amine, US6040112 Examples of the compounds and the like are mentioned in column 3, line 60 of the specification.

(2) Compounds having a nitrogen-containing heterocycle Specific examples of these compounds include 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, N-hydroxyethylpiperidine, bis (1,2,2, 6,6-pentamethyl-4-piperidyl) sebacate, 4-dimethylaminopyridine, antipyrine, hydroxyantipyrine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4 .0] -undec-7-ene and the like.

(3) Amine compounds having a phenoxy group Specific examples of these compounds include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine. And compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of US Patent Application Publication No. 2007/02245539.

(4) Ammonium salts Specific examples of these compounds include tetraalkylammonium hydroxides typified by tetrabutylammonium hydroxide.
The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of the total solid of actinic-ray-sensitive or radiation-sensitive resin composition, Preferably it is 0.01-5 mass%.

  The molar ratio of the photoacid generator / basic compound is preferably 2.5 to 300 (here, “photoacid generator” refers to the repeating unit (A) in the resin (P) described above and the resin. (Including both (P) and a photoacid generator added). That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is 300 or less from the viewpoint of suppressing a decrease in resolution due to the occurrence of pattern thickening over time before post-exposure heat treatment. It is preferable that This molar ratio is more preferably 5.0 to 200, still more preferably 7.0 to 150.

[3] Resin that decomposes by the action of an acid to increase the dissolution rate in an aqueous alkali solution The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is decomposed by the action of an acid and becomes alkaline in addition to the resin (P). You may contain resin which the melt | dissolution rate with respect to aqueous solution increases.

  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 can be obtained by reacting a precursor of a group capable of being reacted or copolymerizing an alkali-soluble resin monomer having an acid-decomposable group bonded thereto with various monomers.

  Specifically, the acid-decomposable group is preferably the same group as the acid-decomposable group described in the above-described resin of the present invention (for example, the acid-decomposable group described in the repeating unit (C) in the resin (P)). As an example.

Examples of the resin having an alkali-soluble group include alkali-soluble resins containing the following repeating units.

  The ratio of the number of repeating units having an acid-decomposable group to the total number of repeating units in the resin is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, still more preferably 0.05 to 0. .40.

  When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains an acid-decomposable resin in addition to the resin (P), the blending amount is 0.1 to 70% by mass in the total solid content of the composition. More preferably, it is 0.1-50 mass%, More preferably, it is 0.1-30 mass%.

[4] Solvent The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a solvent. In particular, a solvent having a normal pressure (760 mmHg) and a boiling point of 150 ° C. or less is preferable.

  Preferred solvents include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), and monoketones that may contain a ring. Examples include organic solvents such as compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

  More preferably usable solvents 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-ethoxypropion. Examples include ethyl acetate, 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.

  The amount of the solvent (including those having a boiling point of 150 ° C. or higher) in the total amount of the composition of the present invention can be appropriately adjusted depending on the desired film thickness, etc. The concentration in the total solid content of the composition is 0.3 to 15% by mass, preferably 0.5 to 8.0% by mass, more preferably 1.0 to 4.0% by mass, and most preferably 1.0 to It is prepared so that it may become 2.0 mass%.

[5] Surfactant The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a surfactant. As the surfactant, a fluorine-based surfactant or a silicon-based surfactant is preferable. Examples include Troisol S-366 manufactured by Co., Ltd., Florard FC430 manufactured by Sumitomo 3M Co., Ltd., and polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

  Examples of other surfactants include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. [6] Acid-decomposable dissolution inhibiting compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is decomposed by the action of an acid to increase the dissolution rate in an alkali developer, and has a molecular weight of 3000 or less. A compound (hereinafter, also referred to as “dissolution inhibiting compound”) can be contained.

  The dissolution inhibiting compound is preferably an alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996). . Examples of the acid-decomposable group and alicyclic structure are the same as those described for the acid-decomposable resin.

Moreover, what contains the structure which substituted the phenolic hydroxyl group of the phenol compound by the acid-decomposable group is also preferable. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.

[7] Other components The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a dye. Suitable dyes include oily dyes and basic dyes.
In order to improve the acid generation efficiency by exposure, a photosensitizer can be further added. Further, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a compound that promotes dissolution in a developer. The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable. Examples of such a phenol compound having a molecular weight of 1000 or less include those described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent 219294.

  In addition, compounds having a proton acceptor functional group described in JP-A No. 2006-208781 and JP-A No. 2007-286574 can be suitably used for the composition of the present application.

[8] Pattern Forming Method The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is applied on a support such as a substrate to form a film. The thickness of the resist film is not particularly limited, but is preferably 0.02 to 0.1 μm, more preferably 0.02 to 0.05 μm, and 0.02 to 0.04 μm. Most preferred.

  As a method of applying the resin composition of the present invention on a substrate, spin coating is preferable, and the number of rotations is preferably 1000 to 3000 rpm.

  For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon, silicon / silicon dioxide coating, silicon nitride) used in the manufacture of precision integrated circuit elements, photomasks, imprint molds, and the like. A quartz substrate having a Cr layer, etc.) is coated and dried by a suitable coating method such as a spinner or a coater to form a film. In addition, a known antireflection film can be applied in advance.

  The film is irradiated with actinic rays or radiation, preferably electron beam (EB), X-ray or EUV light, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.

  In the development step, an alkali developer is usually used. Examples of the alkaline developer of the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Alkaline aqueous solutions of cyclic amines such as quaternary ammonium salts such as pyrrole and pihelidine can be used.

Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

  For details on the production of 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.

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

<Synthesis of Resins P-1 to P-40>
[Synthesis Example 1: Synthesis of Resin P-13]
Resin P-13 was synthesized according to the following scheme.

(Synthesis of Compound (9))
100.00 g of compound (5) was dissolved in 400 g of ethyl acetate. The obtained solution was cooled to 0 ° C., and 47.60 g of sodium methoxide (28 mass% methanol solution) was added dropwise over 30 minutes. This was then stirred at room temperature for 5 hours. Ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with distilled water and then dried over anhydrous sodium sulfate, and the solvent was distilled off. In this way, 131.70 g of Compound (6) (54 mass% ethyl acetate solution) was obtained.

  56.00 g of ethyl acetate was added to 18.52 g of compound (6) (54 mass% ethyl acetate solution). To this, 31.58 g of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride was added and cooled to 0 ° C. A solution prepared by dissolving 12.63 g of triethylamine in 25.00 g of ethyl acetate was added dropwise over 30 minutes, and the mixture was stirred for 4 hours while maintaining the liquid temperature at 0 ° C. Ethyl acetate was added, and the organic layer was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. In this way, 32.90 g of Compound (7) was obtained.

  35.00 g of compound (7) was dissolved in 315 g of methanol, cooled to 0 ° C., 245 g of 1N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 2 hours. After the solvent was distilled off, ethyl acetate was added, and the organic layer was washed 3 times with saturated brine and then dried over anhydrous sodium sulfate, and the solvent was distilled off. In this way, 34.46 g of Compound (8) was obtained.

  28.25 g of compound (8) was dissolved in 254.25 g of methanol, 23.34 g of triphenylsulfonium bromide 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 3 times with distilled water, and then the solvent was distilled off. In this way, 42.07 g of Compound (9) was obtained.

(Synthesis of Resin (P-13))
12.45 g of p-hydroxystyrene (6) (53.1 wt% propylene glycol monomethyl ether solution), 5.71 g of compound (4), 6.77 g of compound (9), and 2.38 g of compound (10) and 1.61 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 35.40 g of propylene glycol monomethyl ether (PGME). 8.85 g of PGME was put in the reaction vessel and dropped into the system at 85 ° C. in a nitrogen gas atmosphere over 2 hours. The reaction solution was heated and stirred for 4 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 33 g of acetone. The diluted solution was dropped into 1000 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and filtered. The filtered solid was washed with 250 g of hexane / ethyl acetate = 8/2. The obtained solid was dissolved in 33 g of acetone and dropped into 600 g of methanol / distilled water = 1/9 to precipitate the polymer, followed by filtration. The filtered solid was washed with 150 g of methanol / distilled water = 1/9. Thereafter, the washed solid was subjected to drying under reduced pressure to obtain 11.31 g of resin P-13.

  Resins P-1 to P-12 and P-14 to P-48 were also synthesized in the same manner as in Synthesis Example 1.

About resin P-1-P-40 synthesize | combined as mentioned above, weight average molecular weight (Mw) and dispersion degree (Mw / Mn) using GPC (the Tosoh Corporation make; HLC-8120; Tsk gel Multipore HXL-M). ) Was measured. The results are shown in Table 2 below. In this GPC measurement, THF was used as a solvent. In Table 2, the position in the table of numerical values representing the composition ratio of each resin corresponds to the position of each repeating unit in the structural formulas of resins P-1 to P-40 shown above from left to right. For example, in the case of the resin P-1, the composition ratios are arranged as 40, 40, 10, 10 from the left in Table 2, but the repeating unit (D) located at the leftmost of the structural formula of P-1 Is 40 parts by mass, the second repeating unit (C) located from the left is 40 parts by mass, the third repeating unit (B) located from the left is 10 parts by mass, and the rightmost repeating unit (A) Means 10 parts by mass.

<Creation of positive resist>
The components shown below (mass% based on the total solid content) are dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 40/60, and the solid content concentration is 1.8 mass%. A solution of was prepared.

Resin P-13 98.29 mass%
Triphenylimidazole 1.70% by mass
PF6320 (Omnova Co., fluorine system) 0.01% by mass
This solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to prepare a chemically amplified positive resist composition (positive resist solution) of Example 1. Similarly, positive resist compositions of Examples 2 to 40 and Comparative Examples 1 to 4 were prepared. The composition of each positive resist composition is shown in Table 3 below.

  In Table 3, the compounds used other than the resin (P) of the examples are shown below.

[Resin used in Comparative Example]

  The molecular weights were all 13,000 and the dispersity was 1.8.

  The composition ratio of the resin is shown below. The numerical values shown below are described in order from the compounds shown on the left in the above chemical formula.

PR-1: 50/40/10
PR-2: 50/50
PR-3: 50/50
PR-4: 65/30/5
[Photoacid generator]

[Organic basic compounds]
N-1: Tetra- (n-butyl) ammonium hydroxide N-2: Tris [2- (2-methoxyethoxy) ethyl] amine N-3: 2,4,5-triphenylimidazole N-4: Tridodecyl Amine [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 type)
[Coating solvent]
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)
SL-3: Ethyl lactate SL-4: Cyclohexanone SL-5: γ-butyrolactone <Pattern formation>
The chemically amplified positive resist composition prepared above is uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 60 seconds to form a film. A positive resist film having a thickness of 50 nm was formed.

  The wafer coated with this positive resist film was subjected to pattern exposure using EUV light (wavelength 13.5 nm, NA 0.3) through a mask having a pitch of 60 nm and a line width of 30 nm. Immediately after the irradiation, the film was heated at 110 ° C. for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) at 23 ° C. for 30 seconds, rinsed with pure water for 15 seconds, and then spin-dried. Thus, a line and space pattern having a pitch of 60 nm and a line width of 30 nm was obtained.

<Resist evaluation>
〔sensitivity〕
The dimension of the resist pattern created by the above method was observed using a scanning electron microscope (S-9380II, manufactured by Hitachi, Ltd.). Irradiation energy when resolving a line and space pattern having a pitch of 60 nm and a line width of 30 nm was defined as sensitivity.

[Pattern shape: film reduction amount in the pattern height direction]
The cross-sectional shape of a line-and-space pattern having a pitch of 60 nm and a line width of 30 nm at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.), and the height direction of the pattern was observed. The amount of film loss was evaluated. More specifically, the pattern height was measured by observing the line pattern from the side, and the film reduction amount was calculated according to the following equation.

[Film reduction amount] = [Coating film thickness 50 nm] − [Pattern height]
It means that the smaller the amount of film reduction, the better the residual film of the pattern and the better the resolution.

[Exposure latitude (EL)]
A dose width that allowed a pattern size of 30 nm ± 10% when the dose showing the sensitivity was changed was determined, and this value was divided by the sensitivity and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

[Line edge roughness (LER)]
The line edge edge roughness is measured by measuring the distance from the reference line where the edge should be at any 50 points of 0.5 μm in the longitudinal direction of a line-and-space pattern with a line width of 30 nm using the scanning electron microscope. The deviation was calculated and 3σ was calculated. The smaller the value, the better the performance. Table 4 shows the results of evaluating the resist compositions of Examples and Comparative Examples as described above. As can be seen from Table 4, it can be said that the resist composition of the present invention has high sensitivity and good LER, exposure latitude, and pattern shape.

Claims (6)

A repeating unit (A) having an ionic structure site that decomposes upon irradiation with actinic rays or radiation to generate acid anions in the side chain of the resin;
A repeating unit (B) represented by the following general formula (B1);
An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having a repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group:

In general formula (B1),
R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, or a cyano group;
Y represents a single bond or a divalent linking group;
Z represents a single bond or a divalent linking group;
Ar represents an aromatic ring group;
p represents an integer of 1 or more. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (B) is a repeating unit represented by the following general formula (B2):

In general formula (B2),
R ₃ represents a hydrogen atom or an alkyl group. The actinic ray-sensitive or radiation-sensitive property according to claim 1, wherein the repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group is a repeating unit represented by the following general formula (C1). Resin composition:

In general formula (C1),
R ₅₃ represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group;
R ₅₄ represents a hydrogen atom;
R ₅₅ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group or an aromatic ring group;
R ₅₆ represents an aromatic ring group;
R ₅₅ and R ₅₆ may combine with each other to form a ring. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the resin (P) further has a repeating unit (D) represented by the following general formula (D3). object.

In general formula (D3),
R ₄₃ represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group;
X ₁ represents a single bond or a divalent linking group;
Ar ₄ represents an (n + 1) -valent aromatic ring group;
n represents an integer of 1 to 4.   An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4.   Forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, exposing the film to EUV light, and developing the exposed film A pattern forming method including: