JP2011215414A - Actinic ray-sensitive or radiation-sensitive resin composition, and pattern forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic ray-sensitive or radiation-sensitive resin composition excellent in coating defect performance, coating film thickness uniformity, and PEBS performance, and provide a pattern forming method using the composition.SOLUTION: The actinic ray-sensitive or radiation-sensitive resin composition includes a structure part (S1) that is decomposed by action of acid to generate alkaline soluble group, resin (P) containing a repeating unit (A) having a structure part (S2) that is decomposed by action of alkali developing solution to increase the dissolution rate into the alkali developing solution, compound for generating acid by irradiation of active light or radiation, and a solvent. At least one kind of solvents listed in the following X group and Y group is contained. The X group includes alkylene glycol monoalkyl ethers, alkyl lactate esters, alkoxy acetic acid alkyls, alkoxy propionic acid alkyls, pyruvic acid alkyls, and acetic acid alkyl ester. The Y group includes cyclic lactones, and alkylene carbonates.

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method using the same. More specifically, the present invention relates to an ultra-microlithographic process applicable to a manufacturing process of a VLSI and a high-capacity microchip, a process for producing a mold for nanoimprinting, a manufacturing process of a high-density information recording medium, and other photofabrication. The present invention relates to a composition suitably used in a process, and a pattern forming method using the composition. In particular, the present invention relates to a composition suitable for exposure using an immersion projection exposure apparatus that uses far ultraviolet light having a wavelength of 300 nm or less as a light source, and a pattern forming method using the same.

  Here, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV) rays, X rays or electron rays (EB). Yes. In the present invention, “light” means actinic rays or radiation.

  In addition, “exposure” means not only light irradiation with a mercury lamp, far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. .

  The chemically amplified resist composition generates an acid in the exposed area by irradiation with radiation such as far ultraviolet light, and the acid-catalyzed reaction changes the solubility of the active radiation irradiated area and non-irradiated area in the developer. And a pattern forming material for forming a pattern on the substrate.

  When a KrF excimer laser is used as an exposure light source, a resin having a basic skeleton of poly (hydroxystyrene) having a small absorption mainly in the 248 nm region is used as a main component. A pattern is formed, which is a better system than the conventional naphthoquinone diazide / novolak resin system.

  On the other hand, when a further short wavelength light source, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group exhibits a large absorption in the 193 nm region. It wasn't.

  For this reason, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed. However, it is extremely difficult to find an appropriate combination of resin, acid generator, additive, solvent, and the like used from the viewpoint of the overall performance as a resist. In particular, when forming a fine pattern with a line width of 100 nm or less, improvement in roughness characteristics and resolution of the line pattern has been demanded.

  In recent years, it has been found that by incorporating a repeating unit having a specific lactone structure into a resin having the alicyclic hydrocarbon structure, roughness characteristics such as line edge roughness can be improved. ing.

  For example, Patent Document 1 describes a resin containing a repeating unit having a structure in which an acid-decomposable group is bonded to a specific position of a norbornane skeleton, and a resist composition containing the same. This document describes that the use of such a composition can improve the pattern shape, exposure margin, and the like.

  Patent Document 2 describes a polymer compound containing a repeating unit having a specific lactone structure having an electron withdrawing group, and a resist composition containing the same. This document describes that such a polymer compound is excellent in solubility in a solvent and hydrolyzability.

  However, from the viewpoint of manufacturing suitability as a resist, in addition to the above performance, it is desired to simultaneously satisfy coating defects, coating film thickness uniformity, and temperature dependency (PEBS performance) after heat processing (PEB).

Japanese Patent No. 4288518 JP 2008-231059 A

  An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition excellent in coating defects, coating film thickness uniformity and PEBS performance, and a pattern forming method using the same.

  For example, the present invention is as follows.

(1) A structural part (S1) that decomposes by the action of an acid to generate an alkali-soluble group, and a structural part (S2) that decomposes by the action of an alkali developer and increases the dissolution rate in the alkali developer. The resin (P) containing the repeating unit (A), a compound that generates an acid upon irradiation with actinic rays or radiation, and an actinic ray-sensitive or radiation-sensitive resin composition containing a solvent, An actinic ray-sensitive or radiation-sensitive resin composition containing at least one of the solvents listed in the following groups X and Y.
(Group X) alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxyacetates, alkyl alkoxypropionates, alkyl pyruvates, alkyl acetates;
(Group Y) Cyclic lactones and alkylene carbonates.

(2) The actinic ray-sensitive or radiation-sensitive resin composition according to (1), further comprising an alkylene glycol monoalkyl ether carboxylate.
(3) The actinic ray-sensitive or radiation-sensitive resin composition according to (2), wherein at least one solvent selected from Group X and at least one solvent selected from Group Y; The actinic ray-sensitive or radiation-sensitive resin composition according to (2), which contains at least three solvents with alkylene glycol monoalkyl ether carboxylates.

  (4) The total content of the solvent selected from the X group and the Y group is 92% by mass or more based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. An actinic ray-sensitive or radiation-sensitive resin composition.

  (5) The actinic ray-sensitive or radiation-sensitive resin according to (4), wherein the total content of the solvent is 95% by mass or more based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Composition.

  (6) The total content of the solvent selected from the X group and the Y group and the alkylene glycol monoalkyl ether carboxylate is 92% by mass or more based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to (2) or (3).

  (7) The actinic ray-sensitive or radiation-sensitive resin according to (6), wherein the total content of the solvent is 95% by mass or more based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Composition.

  (8) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (7), wherein the structural portion (S2) includes a lactone structure.

  (9) The sensation according to any one of (1) to (8), wherein the structural site (S1) is bonded to at least one of two carbon atoms adjacent to the ester group constituting the lactone structure. Actinic ray-sensitive or radiation-sensitive resin composition.

(10) The actinic ray-sensitive or radiation-sensitive resin composition according to (9), wherein the repeating unit (A) has a structure represented by the following general formula.

In Formula (1), R ₂ independently represents a chain or cyclic alkylene group when n ≧ 2. R < ₃ > represents an alkyl group or a cycloalkyl group each independently when k> = 2. When k ≧ 2, at least two of R ₃ may be bonded to each other to form a ring. X represents an alkylene group, an oxygen atom, or a sulfur atom. Y represents the structural unit (S1) independently when m ≧ 2. Z each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond when n ≧ 2. k represents an integer of 0 to 5. m represents an integer of 1 to 5 that satisfies the relationship m + k ≦ 6. n represents an integer of 0 to 5.

  (11) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (10), further comprising a hydrophobic resin.

  (12) A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (11).

  (13) Forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (11), exposing the film, and developing the exposed film A pattern forming method including:

  (14) The pattern forming method according to (13), wherein the exposure is performed through an immersion liquid.

  According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition excellent in coating defect, coating film thickness uniformity, and PEBS performance, and a pattern forming method using the same.

Embodiments of the present invention are described in detail below.
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.

[1] Resin (P)
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention includes a structural site (S1) that decomposes by the action of an acid to generate an alkali-soluble group, and decomposes by the action of an alkali developer, And a resin (P) containing a repeating unit (A) having a structural site (S2) that increases the dissolution rate in the aqueous solution. When such a resin is contained in the composition, it is possible to improve roughness characteristics, exposure latitude, depth of focus, development defect performance, and pattern shape.

[Repeating unit (A)]
The structural site (S2) provided in the repeating unit (A) is not particularly limited, but includes, for example, an aryl ester structure or a lactone structure. The structural site (S2) more preferably contains a lactone structure. By adopting a structure including a lactone structure as the structural portion (S2), for example, it is possible to further improve the substrate adhesion.

When the structural unit (S2) contains a lactone structure, the structural site (S1) is bonded to a ring containing a lactone structure (hereinafter also referred to as a lactone ring) as shown in the following general formula (4). Preferably it is. When such a configuration is employed, for example, the hydrolyzability of the resin and the development defect performance of the composition can be improved.

  In the formula, S1 represents a group corresponding to the structural moiety (S1). A broken line part represents an atomic group necessary for forming a lactone ring together with the ester group.

When the structural site (S2) contains a lactone structure, the structural site (S1) is preferably bonded to at least one of the two carbon atoms adjacent to the ester group constituting the lactone structure. That is, it is preferable that the repeating unit (A) includes a structure represented by the following general formula (4-1) or general formula (4-2). In addition, it is more preferable that the repeating unit (A) includes a structure represented by the following general formula (4-1).

In the formula, S1 represents a group corresponding to the structural moiety (S1). A broken line part represents an atomic group necessary for forming a lactone ring together with the ester group.
By adopting the above configuration, for example, the hydrolyzability of the resin and the development defect performance of the composition can be further improved.

  The structural moiety (S1) is represented by, for example, “-(linking group)-(acid-decomposable group)”. Here, the acid-decomposable group is preferably a group represented by “— (group obtained by removing a hydrogen atom from an alkali-soluble group) — (group capable of leaving by the action of an acid)”.

  Examples of alkali-soluble groups include phenolic hydroxyl groups, carboxy groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl). ) Imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group and tris (alkylsulfonyl) methylene Groups.

  Preferred alkali-soluble groups include carboxy groups, fluorinated alcohol groups, and sulfonic acid groups. As the fluorinated alcohol group, a hexafluoroisopropanol group is particularly preferable.

Examples of the group capable of leaving by the action of an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ) and -C (R ₀₁ ) ( R ₀₂ ) (OR ₃₉ ).
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

  Preferred acid-decomposable groups include, for example, cumyl ester groups, enol ester groups, acetal ester groups and tertiary alkyl ester groups. More preferably, a tertiary alkyl ester group is mentioned.

  The acid-decomposable group preferably contains an alicyclic structure. That is, the resin (P) preferably contains a repeating unit (A) having an acid-decomposable group containing an alicyclic structure. When such a configuration is adopted, for example, etching resistance and resolution can be further improved. The alicyclic structure may be monocyclic or polycyclic.

The structural site (S1) is not particularly limited, but a group represented by the following general formula (S1-1) is more preferable.

Where
Z ₂₁ represents a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or And represents a combination of these.
L ₂ 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, two or more groups to be combined may be the same or different from each other. Further, the two or more groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group And may be linked via a linking group selected from the group consisting of a combination thereof.
R ₄ represents an alkyl group.
R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group. R ₅ and R ₆ may be bonded to each other to form a ring.

In —NR— as Z ₂₁ , the alkyl group represented by R may be linear or branched. Moreover, this alkyl group may have a substituent. Examples of the alkyl group represented by R include carbon such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group. An alkyl group having a number of 20 or less is exemplified, an alkyl group having a carbon number of 8 or less is more preferred, and an alkyl group having a carbon number of 3 or less is particularly preferred. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

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. Specific examples include divalent linking groups having the following structure.

Z ₂₁ includes a single bond, —O—, —OCO—, —COO—, —OSO ₂ —, —SO ₃ —, —CONR—, or —CO— and a divalent nitrogen-containing non-aromatic heterocyclic ring. A group in combination with a group is preferable, a single bond, —COO—, —SO ₃ — or —CONR— is more preferable, and a single bond or —COO— is particularly preferable.

The alkylene group in L ₂ may be linear or branched. As this alkylene group, Preferably, C1-C8 things, such as a methylene group, ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, are mentioned. The alkylene group in L ₂ is more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.

Examples of the alkenylene group in L ₂ include a group having a double bond at an arbitrary position of the alkylene group described above.

The cycloalkylene group in L ₂ may be monocyclic or polycyclic. Preferred examples of the cycloalkylene group include those having 3 to 17 carbon atoms such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, and a diamantylene group. The cycloalkylene group in L ₂ is more preferably a cycloalkylene group having 5 to 12 carbon atoms, and particularly preferably a cycloalkylene group having 6 to 10 carbon atoms.

Examples of the divalent aromatic ring group in L ₂ include arylene groups having 6 to 14 carbon atoms such as a phenylene group, a tolylene group, and a naphthylene group, or thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, and imidazole. , Divalent aromatic ring groups containing heterocycles such as benzimidazole, triazole, thiadiazole and thiazole. These divalent aromatic ring groups may have a substituent.

L ₂ is preferably a single bond, an alkylene group, a cycloalkylene group, a group in which an alkylene group and a cycloalkylene group are combined, or a group in which an alkylene group and a divalent aromatic ring group are combined. Alternatively, a cycloalkylene group is more preferable, and a single bond or an alkylene group is particularly preferable.

In the general formula (1), it is also preferable that both Z ₂₁ and L ₂ are single bonds. That is, the structural site (S1) is also preferably a group represented by the following formula (S1-2). When such a configuration is adopted, the glass transition temperature (Tg) of the resin is increased, and for example, the exposure latitude can be further improved.

In formula (S1-2), each of R ₄ , R ₅ and R ₆ has the same meaning as that described above for general formula (S1-1).

Hereinafter, R _{4 to} R ₆ in Formulas (S1-1) and (S1-2) will be described.

The alkyl group in R ₄ , R ₅ or R ₆ may be linear or branched. Moreover, these alkyl groups may have a substituent. Examples of the alkyl group in R ₄ or R ₅ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group. And an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, and particularly preferably an alkyl group having 3 or less carbon atoms.

The cycloalkyl group for R ₅ or R ₆ may be monocyclic or polycyclic. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a diadamantyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. As a cycloalkyl group, a C3-C20 thing is preferable and a C5-C10 thing is more preferable.

The ring that R ₅ and R ₆ may be bonded to each other is preferably a ring having 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, Polycyclic ones such as an adamantyl group, a tetracyclodecanyl group and a tetracyclododecanyl group may be used. When R ₅ and R ₆ are bonded to each other to form a ring, R ₄ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

One of R ₅ and R ₆ is preferably an adamantyl group. That is, the structural site (S1) preferably has a structure represented by the following formula. The following formula shows the structure when R ₆ is an adamantyl group.

Wherein, _{R 4} and _{R 5} are as defined above in connection with general formula (S1-1) and (S1-2).

R ₅ and R ₆ are also preferably bonded to each other to form a ring. This ring has a structure represented by the following formula, for example.

Wherein, _{R 4} has the same meaning as _{R 4} in the general formula (S1-1) and (S1-2).
n is an integer of 1-5. n is preferably 3 or 4. That is, the ring formed by combining R ₅ and R ₆ with each other is preferably a 5-membered ring or a 6-membered ring.
Specific examples of the structural site (S1) are shown below.

  When the structural site (S2) contains a lactone structure, the lactone structure is preferably a 5- to 7-membered lactone structure. In addition, another ring structure may be condensed with this 5- to 7-membered ring lactone structure so as to form a bicyclo structure or a spiro structure.

Examples of the lactone structure include structures represented by the following general formulas (LC1-1) to (LC1-17). Among these, a structure represented by (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13) or (LC1-14) is more preferable, (LC1 -4) or the structure represented by (LC1-5) is particularly preferable.

  The lactone structure may further have a substituent other than the structural site (S1). Preferred substituents include, for example, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxy group, and a halogen. An atom, a hydroxyl group, and a cyano group are mentioned.

  The repeating unit having a lactone structure 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 thereof is preferably 90% ee or more, more preferably 95% ee or more.

The repeating unit (A) preferably has a structure represented by the following general formula (1).

In the formula, each R ₃ independently represents an alkyl group or a cycloalkyl group when k ≧ 2. When k ≧ 2, at least two of R ₃ may be bonded to each other to form a ring.
X represents an alkylene group, an oxygen atom, or a sulfur atom.
Y represents the structural unit (S1) described above independently when m ≧ 2.
k represents an integer of 0 to 5.
m represents an integer of 1 to 5 that satisfies the relationship m + k ≦ 6.

R ₃ represents an alkyl group or a cycloalkyl group as described above. These alkyl groups or cycloalkyl groups may further have a substituent.
The alkyl group for R ₃ preferably has 1 to 30 carbon atoms, and more preferably 1 to 15 carbon atoms. The alkyl group for R ₃ may be linear or branched.
Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, an n-tetradecyl group, and the like. An n-octadecyl group is mentioned.
Examples of the branched alkyl group include isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group.

The cycloalkyl group for R ₃ may be monocyclic or polycyclic. A part of carbon atoms in the cycloalkyl group represented by R ₃ may be substituted with a heteroatom such as an oxygen atom.
The cycloalkyl group represented by R ₃ preferably has 3 to 20 carbon atoms. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

Examples of the substituent that the alkyl group or cycloalkyl group of R ₃ may have include halogen atoms such as fluorine atom, chlorine atom and bromine atom; mercapto group; hydroxy group; methoxy group, ethoxy group, isopropoxy group, t -Butoxy group and alkoxy group of benzyloxy group; alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, pentyl group and hexyl group; cyclopropyl group, Cyclobutyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group; cyano group; nitro group; sulfonyl group; silyl group; ester group; acyl group; vinyl group;

When k ≧ 2, at least two of R ₃ may be bonded to each other to form a ring. The group formed by bonding at least two of R ₃ to each other is preferably a cycloalkylene group.

  X represents an alkylene group, an oxygen atom, or a sulfur atom as described above. This alkylene group may further have a substituent.

  The alkylene group for X is preferably one having 1 or 2 carbon atoms. That is, the alkylene group of X is preferably a methylene group or an ethylene group.

  Examples of the substituent which the alkylene group of X may have include, for example, halogen atoms such as fluorine atom, chlorine atom and bromine atom; mercapto group; hydroxy group; methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyl Alkoxy group of oxy group; alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, pentyl group and hexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group Cycloalkyl group such as cyclohexyl group and cycloheptyl group; cyano group; nitro group; sulfonyl group; silyl group; ester group; acyl group; vinyl group;

  Y represents the structural part (S1) described above. As described above, the structural site (S1) is preferably represented by the general formula (S1-1) or (S1-2).

  k represents an integer of 0 to 5 as described above. k is preferably an integer of 0 to 3.

  As described above, m represents an integer of 1 to 5 that satisfies the relationship m + k ≦ 6. m is preferably an integer of 1 to 3, particularly preferably 1.

In the structure represented by the general formula (1), Y is preferably bonded to at least one of two carbon atoms adjacent to the ester group constituting the lactone structure. In particular, at least one of Y is preferably bonded to the α-position of the carbonyl carbon of the ester group. That is, the structure represented by the general formula (1) is particularly preferably represented by the following general formula (1α).

In general formula (1α), R 3, X, Y, k and m have the same meanings as in general formula (1).
The repeating unit (A) is particularly preferably a repeating unit represented by the following general formula (A1).

Where
R ₁₁ each independently represents a hydrogen atom, an alkyl group or a halogen atom.

L ₁ each independently 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 of these when n ≧ 2. In the combined group, two or more groups to be combined may be the same or different from each other. Further, the two or more groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group And may be linked via a linking group selected from the group consisting of a combination thereof.

Z ₁₁ and Z ₁₂ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (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.
n represents an integer of 0 to 5.
R ₃ , X, Y, k, and m have the same meaning as in General Formula (1).

As an alkyl group in R < ₁₁ >, a C1-C5 thing is preferable and a methyl group is especially preferable. The alkyl group of R ₁ may further have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, and an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, and a benzyloxy group. R ₁ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group.

The alkylene group in L ₁ may be linear or branched. As this alkylene group, Preferably, C1-C8 things, such as a methylene group, ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, are mentioned. The alkylene group in L ₁ is more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.

Examples of the alkenylene group in L ₁ include a group having a double bond at an arbitrary position of the alkylene group described above.

The cycloalkylene group in L ₁ may be monocyclic or polycyclic. Preferred examples of the cycloalkylene group include those having 3 to 17 carbon atoms such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, and a diamantylene group. The cycloalkylene group in L ₁ is more preferably a cycloalkylene group having 5 to 12 carbon atoms, and particularly preferably a cycloalkylene group having 6 to 10 carbon atoms.

Examples of the divalent aromatic ring group in L ₁ include arylene groups having 6 to 14 carbon atoms such as a phenylene group, a tolylene group, and a naphthylene group, or thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole. , Divalent aromatic ring groups containing heterocycles such as benzimidazole, triazole, thiadiazole and thiazole. These divalent aromatic ring groups may have a substituent.

L ₁ is preferably a single bond, a cycloalkylene group, a group obtained by combining a cycloalkylene group and an alkylene group, a divalent aromatic ring group, or a group obtained by combining a divalent aromatic ring group and an alkylene group, A single bond, a cycloalkylene group or a divalent aromatic ring group is more preferred, and a single bond or a cycloalkylene group is particularly preferred.

In —NR— as Z ₁₁ and Z ₁₂ , the alkyl group represented by R may be linear or branched. Moreover, this alkyl group may have a substituent. Examples of the alkyl group represented by R include carbon such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group. An alkyl group having a number of 20 or less is exemplified, an alkyl group having a carbon number of 8 or less is more preferred, and an alkyl group having a carbon number of 3 or less is particularly preferred. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

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, the same divalent linking groups as mentioned above for Z ₂₁ in formula (S1-1) can be given.

Z ₁₁ is preferably a single bond, —COO—, —OCO—, —SO ₃ —, —CONR—, or a combination of —CO— and a divalent nitrogen-containing non-aromatic heterocyclic group, A single bond, -COO-, -CONR-, or a combination of -CO- and a divalent nitrogen-containing non-aromatic heterocyclic group is more preferred, and -COO- or -CONR- is particularly preferred.

Z ₁₂ is preferably a single bond, —O—, —OCO—, —COO—, —OSO ₂ —, —CONR—, or —NRCO—, and is preferably a single bond, —O—, —OCO—, —COO—. Or -CONR- is more preferable, and a single bond, -O-, -OCO- or -COO- is particularly preferable.

  n represents an integer of 0 to 5, and may be 0 or an integer of 1 to 5. In the former case, the glass transition temperature (Tg) of the resin (P) is increased, and for example, the exposure latitude can be further improved. In the latter case, it is possible to further improve the solubility of the resin (P) in the developer. n is preferably an integer of 0 to 3.

The repeating unit (A) is more preferably represented by the following general formula (A2).

In general formula (A2),
X, R ₃ and k have the same meanings as in general formula (1).
Z ₂₁ , L ₂ , R ₄ , R ₅ and R ₆ have the same meanings as those in General Formula (S1-1).
R ₁₁ , L ₁ , Z ₁₁ , Z ₁₂ and n are as defined in general formula (A1).

  The resin (P) containing the repeating unit represented by the general formula (A2) is made to polymerize a compound corresponding to the general formula (A2), or to copolymerize this compound and another monomer. Is obtained.

The compound corresponding to the general formula (A2) can be synthesized according to a conventional method. For example, the polymerizable compound represented by the following general formula (3M) can be synthesized by the following scheme.

In General Formula (3M), R _1a has the same meaning as R 11 in General Formula (A2). R ₃ , R ₄ , R ₅ , R ₆ , X, k, and n are as defined in general formula (A2). l represents an integer of 1 to 5. When n is an integer of 1 to 5, l is preferably 1.

  In the above scheme, first, a cyano group is converted to a carboxy group by hydrolyzing the cyanolactone represented by the above formula. Thereby, the carboxylic acid represented by the general formula (3M-1) is obtained.

Next, the compound represented by the general formula (3M-2) is obtained by reacting the carboxylic acid represented by the general formula (3M-1) with an alcohol.
This reaction is performed, for example, by sequentially or simultaneously adding a carboxylic acid represented by the general formula (3M-1), an alcohol, a base, and a condensing agent in a solvent. At this time, the reaction system may be cooled or heated as necessary.
Examples of the solvent for this reaction include tetrahydrofuran, chloroform, dichloroethane, ethyl acetate, and acetonitrile. Examples of the base include 4-dimethylaminopyridine. Examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-diisopropylcarbodiimide, N- (tert-butyl) -N ′. -Ethylcarbodiimide and N, N'-di (ter-butyl) carbodiimide.

  Subsequently, the alcohol represented by the general formula (3M-2) is reacted with the polymerizable site to obtain an ester represented by the general formula (3M-3). This polymerizable site can be easily introduced by a known method.

For example, when the polymerizable site is an acid chloride such as methacrylic acid chloride and norbornenecarboxylic acid chloride, the above reaction is performed, for example, as follows. That is, the above reaction is performed, for example, by sequentially or simultaneously adding an alcohol represented by the general formula (3M-2), the above acid chloride, and a base in a solvent. At this time, the reaction system may be cooled or heated as necessary.
Examples of the solvent for this reaction include tetrahydrofuran, acetonitrile, ethyl acetate, diisopropyl ether, and methyl ethyl ketone. Examples of the base include triethylamine, pyridine, and 4-dimethylaminopyridine.

Alternatively, when the polymerizable site is carboxylic acid such as methacrylic acid and norbornene carboxylic acid, the above reaction is performed, for example, as follows. That is, said reaction is performed by mixing and heating the alcohol represented by general formula (3M-2), said carboxylic acid, and an inorganic acid and / or organic acid in a solvent, for example. This reaction may be performed while removing water generated by the reaction from the system.
Examples of the solvent for this reaction include toluene and hexane. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid. Examples of the organic acid include p-toluenesulfonic acid and benzenesulfonic acid.

Next, the ester represented by the general formula (3M-3) is hydrolyzed. In this way, the carboxylic acid represented by the general formula (3M-4) is obtained.
This hydrolysis reaction is performed, for example, by sequentially or simultaneously adding an ester represented by the general formula (3M-3) and a base in a solvent. At this time, the reaction system may be cooled or heated as necessary.
Examples of the solvent for this reaction include acetone, tetrahydrofuran, acetonitrile, and water. Examples of the base include sodium hydroxide and potassium carbonate.

  Then, the acid site | part of the carboxylic acid represented by general formula (3M-4) is converted into an acid chloride, and the acid chloride represented by general formula (3M-5) is obtained. This reaction is performed, for example, by sequentially or simultaneously adding a carboxylic acid represented by the general formula (3M-4) and thionyl chloride. At this time, the reaction system may be cooled or heated as necessary. Further, a solvent such as benzene and dichloromethane and / or a catalyst such as dimethylformamide, hexamethylphosphoric triamide and pyridine may be further added.

  Finally, the acid chloride represented by the general formula (3M-5) is reacted with the corresponding alcohol to obtain the compound represented by the general formula (3M). The reaction between the acid chloride and the alcohol can be performed in the same manner as the synthesis of the compound represented by the general formula (3M-3) described above.

  The content of the repeating unit (A) is preferably 15 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, based on all repeating units in the resin. .

Specific examples of the repeating unit (A) are given below. In the specific examples below, R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom. R ₁ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a trifluoromethyl group or a halogen atom.

[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.

  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 1 to 4 with respect to all the repeating units in the resin (P). The range of 70 mol% is preferable, and the range of 5 to 50 mol% is more preferable.

[Repeating unit (C)]
The resin (P) may have a repeating unit (C) having a group which is different from the repeating unit (A) and decomposes under the action of an alkali developer to increase 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 optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).
Preferable substituents that the alkyl group of 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. Preferably a single _bond, -Ab 1 -CO ₂ - is a divalent linking group represented by.
Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene 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. V is more preferably a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-17) listed above. In addition to the repeating unit (C), the resin (P) may further contain a repeating unit in which a lactone structure is directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14). By using a specific lactone structure, line edge roughness and development defect performance are improved.

  The lactone structure may have an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group, an alkoxy group, or the like as a substituent.

The repeating unit represented by the general formula (AII) is preferably a repeating unit represented by the following general formula (III-1).

In general formula (III-1),
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof independently when there are a plurality of R ₀ .
When there are a plurality of Zs, each independently represents an ether bond, an ester bond, an amide bond, or a urethane bond.

Or urea bond

Represents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
n _is the repetition number of the structure represented by -R 0 -Z-, represents an integer of 0 to 5.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

R ₉ independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, when there are a plurality of R _{9 s} , May be formed.

X represents an alkylene group, an oxygen atom or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5. m is preferably 0 or 1.

The alkyl group for R ₉ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. These groups may have a substituent, and examples of the substituent include an alkoxy group such as a hydroxy group, a methoxy group, and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom. R ₉ is more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.

  Examples of the alkylene group for X include a methylene group and an ethylene group. X is preferably an oxygen atom or a methylene group, more preferably a methylene group.

When m is 1 or more, at least one R ₉ is preferably substituted at the α-position or β-position of the carbonyl group of the lactone, particularly preferably at the α-position.

  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 1 to 60 mol% with respect to all the repeating units. Preferably it is the range of 2-50 mol%, More preferably, it is the range of 5-50 mol%. One type of repeating unit (C) may be used, or two or more types may be used in combination.

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) may further have a repeating unit having a hydroxyl group or a cyano group other than the above-mentioned repeating unit (A), repeating unit (B) and repeating unit (C). As a result, substrate adhesion and developer compatibility can be improved.

The repeating unit (D) 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 _{2c to} R _4c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R _{2c to} R _4c represents a hydroxyl group or a cyano group. Preferably, one or two of R _{2c to} R _4c are a hydroxyl group and the remaining is a hydrogen atom. In general formula (VIIa), it is more preferable that two _{members out} of R _{2c to} R _4c are hydroxyl groups and the remaining 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), R1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R _<2c > -R < _4c > is synonymous with R _{< 2c} > -R < _4c > in general formula (VIIa)-(VIIc).

  When the resin (P) contains the repeating unit (D), the content of the repeating unit (D) having a hydroxyl group or a cyano group is preferably 1 to 40 mol% with respect to all the repeating units in the resin (P). More preferably, it is 2-30 mol%, More preferably, it is 5-25 mol%.

Specific examples of the repeating unit (D) having a hydroxyl group or a cyano group will be given below, but the present invention is not limited thereto.

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, it is preferably a repeating unit having an aromatic ring group and an alkali-soluble group. The structure represented by IV) is more preferable.

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.
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.

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.

The resin (P) may further have a repeating unit that has an alicyclic hydrocarbon structure having no polar group and does not exhibit acid decomposability. Examples of such a repeating unit include 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.

  When the resin (P) has a repeating unit that has an alicyclic hydrocarbon structure having no polar group and does not exhibit acid decomposability, the content of this repeating unit is the total repeating unit in the resin (P). The content is preferably 1 to 40 mol%, more preferably 2 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 .

In addition to the above repeating structural units, the resin (P) of the present invention has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and generally required characteristics 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 formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

    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 molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist performance required. It is appropriately set to adjust the resolving power, heat resistance, sensitivity and the like.

  Moreover, when the composition of this invention contains the hydrophobic resin mentioned later, it is preferable that resin (P) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin.

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. Also, unsaturated monomers corresponding to the precursors of each structure
It is also possible to obtain a desired resin by polymerizing after polymerization using a polymer.

  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 usually 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).

  As for resin (P), it is natural that there are few impurities, such as a metal, It is preferable that the residual amount of a monomer and an oligomer component is 0-10 mass%, and it is more preferable that it is 0-5 mass%. The content is preferably 0 to 1% by mass. As a result, the amount of foreign matter in the liquid can be reduced, and changes over time such as sensitivity can be reduced.

  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 200000, more preferably in the range of 2000 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 1,000 to 200,000, heat resistance and dry etching resistance can be prevented from being deteriorated, and developability is deteriorated, and viscosity is increased to prevent film formation from being deteriorated. be able to. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: tetrahydrofuran (THF)).

  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 99% by mass, more preferably 60 to 95% by mass, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention.

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

[2] Solvent The composition of the present invention includes, as a solvent, alkylene glycol monoalkyl ethers, alkyl lactate esters, cyclic lactones, alkylene carbonates, alkyl alkoxyacetates, alkyl alkoxypropionates, alkyl pyruvates, And at least one solvent selected from alkyl acetates.

  Examples of the alkylene glycol monoalkyl ethers include propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, Preferred is ethylene glycol monoethyl ether. More preferred are propylene glycol monomethyl ether and propylene glycol monoethyl ether, and particularly preferred is propylene glycol monomethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate. Particularly preferred is ethyl lactate.
Preferred examples of alkyl alkoxypropionates include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of cyclic lactones include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octa Neuk lactone and α-hydroxy-γ-butyrolactone are preferred. Particularly preferred is γ-butyrolactone.

Preferred examples of the alkylene carbonates include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate. Particularly preferred is propylene carbonate.
Alkoxyacetic acid alkyls include, for example, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy acetate. Preferred is 2-propyl.

Preferred examples of alkyl pyruvates include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
Examples of the alkyl acetates include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, amyl acetate and the like, and particularly preferably butyl acetate.

In one embodiment of the present invention, the solvent includes, in addition to at least one selected from the above solvents, mixed alkylene glycol monoalkyl ether carboxylates containing at least one alkylene glycol monoalkyl ether carboxylate, for example, propylene Glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol Preferred is monoethyl ether acetate.

  As the alkylene glycol monoalkyl ether carboxylates, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate are more preferable, and propylene glycol monomethyl ether acetate is particularly preferable.

  Preferred blending ratios in the mixed solvent are as follows. That is, all solvents of solvents selected from alkylene glycol monoalkyl ethers, alkyl lactate esters, cyclic lactones, alkylene carbonates, alkyl alkoxyacetates, alkyl alkoxypropionates, alkyl pyruvates, and alkyl acetates The total blending ratio is preferably in the range of 10 to 60% by mass, and more preferably in the range of 20 to 60% by mass. In addition, the blending ratio of the alkylene glycol monoalkyl ether carboxylates in all the solvents is preferably in the range of 40 to 90% by mass, and more preferably in the range of 40 to 80% by mass.

In another embodiment of the present invention, the solvent is at least three kinds of at least one solvent selected from the following group X, at least one solvent selected from group Y, and alkylene glycol monoalkyl ether carboxylates. A mixed solvent containing a solvent is preferred.
(Group X) alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxyacetates, alkyl alkoxypropionates, alkyl pyruvates, and alkyl acetates;
(Group Y) Cyclic lactones and alkylene carbonates.

  Specific examples and preferred solvents of the solvents included in the X group and the Y group, and the alkylene glycol monoalkyl ether carboxylates are as described above.

  The preferable compounding ratio in the mixed solvent is as follows. That is, the blending ratio of the Y group solvent in all the solvents is preferably in the range of 0.5 to 10% by mass, more preferably in the range of 0.5 to 4% by mass, More preferably, it is in the range of 2% by mass. And the compounding ratio of the solvent of the X group and the compounding ratio of the alkylene glycol monoalkyl ether carboxylates are 10 to 60% by mass of the solvent of the X group based on the mixed solvent obtained by removing the solvent of the Y group from all the solvents. The range is preferable, and the range of 20 to 60% by mass is more preferable. Further, the blending ratio of the alkylene glycol monoalkyl ether carboxylates is preferably in the range of 40 to 90% by mass, and more preferably in the range of 40 to 80% by mass.

  In the present invention, when the content of the solvent does not contain alkylene glycol monoalkyl ether carboxylates, the total mass of the composition of the present invention is the total content of the solvent selected from the group X and group Y. Is preferably 92% by mass or more, and more preferably 95% by mass or more. When the alkylene glycol monoalkyl ether carboxylates are not included, the total content of the solvent selected from the group X and the group Y and the alkylene glycol monoalkyl ether carboxylates is included in the total mass of the composition of the present invention. On the other hand, 92 mass% or more is preferable and 95 mass% or more is more preferable.

[3] Compound that generates an acid upon irradiation with actinic rays or radiation The composition according to the present invention contains a compound that generates an acid upon irradiation with an actinic ray or radiation (an acid generator). As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, or irradiation with actinic ray or radiation used for micro-resist etc. Known compounds that generate acids and mixtures thereof can be appropriately selected and used.

  Examples of the acid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

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

Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712, etc. can also be used.
Preferred examples of the acid generator include compounds represented by the following general formula (ZI), (ZII) or (ZIII).

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

Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

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

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

  The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms such as methyl. Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group and the like.

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

  The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy group , Hydroxy group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group (Preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl A group (preferably having a carbon number of 1 to 15), an alkyliminosulfonyl group (preferably having a carbon number of 2 to 15), Reeloxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

Moreover, the anion which produces the acid represented with the following general formula (IA) as a preferable sulfonate anion can also be mentioned.

In the formula, each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, and R ¹ and R ² in the case where a plurality of R ¹ and R ^{2 are present.} May be the same or different. L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same or different. A represents a group having a cyclic structure. x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

General formula (IA) is demonstrated in detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, a fluorine atom and CF ₃ are preferable.

The alkyl group in R ¹ and R ^{2 and} the alkyl group substituted with at least one fluorine atom are preferably those having 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specifically, CF ₃ is preferable.

y is preferably 0 to 4, and more preferably 0. x is preferably from 1 to 8, and preferably from 1 to 4. z is preferably 0 to 8, particularly preferably 0 to 4. The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, Examples include alkenylene groups. Among these, —COO—, —OCO—, —CO—, —O—, and —SO ₂ — are preferable, and —COO—, —OCO—, and —SO ₂ — are more preferable.

  The group having a cyclic structure of A is not particularly limited as long as it has a cyclic structure. The group having an alicyclic group, an aryl group, or a heterocyclic structure (not only those having an aromatic attribute, but also having an aromatic attribute). And the like).

  The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group. A polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is used in the PEB (post-exposure heating) step. It is preferable from the viewpoint of improving MEEF (mask error enhancement factor) because diffusibility in the film can be suppressed.

  Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Of these, naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm.

  The group having a heterocyclic structure may be monocyclic or polycyclic, and includes a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, a piperidine ring, and a decahydroisoquinoline ring. It is done. Of these, a furan ring, a thiophene ring, a pyridine ring, a piperidine ring, and a decahydroisoquinoline ring are preferable. Further, the heterocyclic structure may be a ring structure having a lactone structure.

  The group having the cyclic structure may have a substituent, and the substituent may be an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), Examples thereof include an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group.

  Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.

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

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

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

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl. Group, sec-butyl group, pentyl group, neopentyl group and the like. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Alkyl groups substituted with fluorine atoms are preferred.

  The two alkyl groups in the bis (alkylsulfonyl) imide anion may be the same or different. Similarly, the plurality of alkyl groups in the tris (alkylsulfonyl) methide anion may be the same or different.

In particular, examples of the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion include anions represented by the following general formula (A3) or (A4).

In general formulas (A3) and (A4),
Y is an alkylene group substituted with at least one fluorine atom, preferably an alkylene group having 2 to 4 carbon atoms. An oxygen atom may be contained in the alkylene chain. A perfluoroalkylene group having 2 to 4 carbon atoms is more preferable, and a tetrafluoroethylene group, a hexafluoropropylene group, and an octafluorobutylene group are most preferable.

  R in the formula (A4) represents an alkyl group or a cycloalkyl group. In addition, the alkylene chain in the alkyl group or cycloalkyl group may contain an oxygen atom.

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

Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI) include, for example, a compound (ZI-1), (ZI-2), (ZI-3) or (ZI-4) described later. The corresponding groups can be mentioned.

The acid generator may be a compound having a plurality of structures represented by the general formula (ZI). For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI), the structures attached to at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferred (ZI) components include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

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

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include 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.

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

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

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

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

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

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

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

The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxy group, a cyano group, or a nitro group.

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

In general formula (ZI-3),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a halogen atom or a phenylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom and a sulfur atom. , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.

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

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

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

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

The aryl group as R _6c and R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

When R _6c and R _7c are combined to form a ring, the group formed by combining R _6c and R _7c is preferably an alkylene group having 2 to 10 carbon atoms, such as ethylene group, propylene Group, butylene group, pentylene group, hexylene group and the like. The ring formed by combining R _6c and R _7c may have a hetero atom such as an oxygen atom in the ring.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c .

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .
Examples of the alkoxy group in the alkoxycarbonylalkyl group include the same alkoxy groups as in R _{1c to} R _5c , and examples of the alkyl group include an alkyl group having 1 to 12 carbon atoms, preferably 1 to 1 carbon atom. 5 straight chain (for example, methyl group and ethyl group).

  The allyl group is not particularly limited, but is preferably an allyl group which is unsubstituted or substituted with a monocyclic or polycyclic cycloalkyl group.

  Although there is no restriction | limiting in particular as a vinyl group, It is preferable that it is a vinyl group substituted by the unsubstituted or monocyclic or polycyclic cycloalkyl group.

As the ring structure that R _x and R _y may be bonded to each other, divalent R _x and R _y (for example, a methylene group, an ethylene group, a propylene group, and the like) are represented by the general formula (ZI-3). A 5-membered or 6-membered ring formed with a sulfur atom, particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring).

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

Specific examples of the cation moiety of compound (ZI-3) are shown below.

The compound (ZI-4) is a compound represented by the following general formula (ZI-4).

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxy group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.

When there are a plurality of R _{14 s,} each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a monocyclic or polycyclic cycloalkyl skeleton. Represents a group having These groups may have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. These groups may have a substituent.

  l represents an integer of 0-2.

  r represents an integer of 0 to 8.

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

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n -An octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group etc. can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are preferable.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, norbornyl, tricyclo Examples include decanyl, tetracyclodecanyl, adamantyl and the like, and cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl are particularly preferable.

The alkoxy group of R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n -Butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group and the like can be mentioned. Of these alkoxy groups, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and the like are preferable.

The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, i- Propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, Examples include n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group and the like. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

Examples of the group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. Can be mentioned. These groups may further have a substituent.

The monocyclic or polycyclic cycloalkyloxy group for R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, It is preferable to have a cycloalkyl skeleton. The monocyclic cycloalkyloxy group having 7 or more carbon atoms is cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloptyloxy group, cyclooctyloxy group, cyclododecanyloxy group, etc. Optionally substituted with methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, 2-ethylhexyl, isopropyl, sec-butyl, t -Alkyl group such as butyl group and iso-amyl group, hydroxy group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamido group, methoxy group, ethoxy group, hydroxyethoxy group , Alkoxy groups such as propoxy group, hydroxypropoxy group, butoxy group, meth Monocyclic cycloalkyloxy having substituents such as alkoxycarbonyl groups such as xoxycarbonyl group, ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group And a group having a total carbon number of 7 or more in combination with an arbitrary substituent on the cycloalkyl group.

  Examples of the polycyclic cycloalkyloxy group having a total carbon number of 7 or more include a norbornyloxy group, a tricyclodecanyloxy group, a tetracyclodecanyloxy group, an adamantantyloxy group, and the like.

The alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, An alkoxy group having a monocyclic cycloalkyl skeleton is preferable. The alkoxy group having a total of 7 or more carbon atoms and having a monocyclic cycloalkyl skeleton is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropoxy, A monocyclic cycloalkyl group that may have the above-mentioned substituents is substituted on an alkoxy group such as sec-butoxy, t-butoxy, iso-amyloxy, etc., and the total carbon number including the substituents is 7 or more Represents things. Examples include a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, and the like, and a cyclohexylmethoxy group is preferable.

  Examples of the alkoxy group having a polycyclic cycloalkyl skeleton having 7 or more carbon atoms include norbornyl methoxy group, norbornyl ethoxy group, tricyclodecanyl methoxy group, tricyclodecanyl ethoxy group, tetracyclo A decanyl methoxy group, a tetracyclodecanyl ethoxy group, an adamantane methoxy group, an adamantane ethoxy group, etc. are mentioned, and a norbornyl methoxy group, a norbornyl ethoxy group, etc. are preferable.

The alkyl group of the alkyl group of R ^14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ are linear, branched, or cyclic, and preferably those having 1 to 10 carbon atoms, such as methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl. Group, n-butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group, neopentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group n -Nonanesulfonyl group, n-decanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group, etc. can be mentioned. Of these alkylsulfonyl groups and cycloalkylsulfonyl groups, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, a cyclohexanesulfonyl group, and the like are preferable.

  Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and alkoxycarbonyloxy. Groups and the like.

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, Examples thereof include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as a cyclohexyloxy group.

  Examples of the alkoxyalkyl group include straight chain having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group. Examples thereof include a chain, branched or cyclic alkoxyalkyl group.

  Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t Examples thereof include linear, branched or cyclic alkoxycarbonyl groups having 2 to 21 carbon atoms such as butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl and the like.

  Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, an n-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, and a cyclopentyloxy group. Examples thereof include linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyloxy group and cyclohexyloxycarbonyloxy.

The ring structure which two R ₁₅ may combine with each other is a 5-membered or 6-membered ring formed by two divalent R ₁₅ together with the sulfur atom in the general formula (ZI-4). Particularly preferred is a 5-membered ring (that is, a tetrahydrothiophene ring), which may be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, and the like. Groups and the like. R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two R ^15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxy group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.
Specific examples of the cation moiety of compound (ZI-4) are given below.

Next, the general formulas (ZII) and (ZIII) will be described.
In formula (ZII), (ZIII), R 204 ~R 207 each independently represents an aryl group, an alkyl group or a cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like.

The alkyl group and cycloalkyl group in R _{204 to} R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxy group, and a phenylthio group.

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

Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.

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

  A represents an alkylene group, an alkenylene group or an arylene group.

  Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.

  Further, the acid generator is preferably a compound that generates an acid having one sulfonic acid group or imide group, more preferably a compound that generates monovalent perfluoroalkanesulfonic acid, or a monovalent fluorine atom or fluorine atom. A compound that generates an aromatic sulfonic acid substituted with a group that contains a monovalent fluorine atom or an imido acid that is substituted with a group containing a fluorine atom, and even more preferably, a fluorinated compound It is a sulfonium salt of a substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted imide acid or a fluorine-substituted methide acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid or a fluorinated substituted imido acid whose pKa of the generated acid is pKa = -1 or less, and the sensitivity is improved. .

  When the composition according to the present invention contains an acid generator, the acid that can be generated by the acid generator may or may not have a fluorine atom. For example, when the acid generator includes an anion, the anion may have a fluorine atom or may not have a fluorine atom.

Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 17.5% by mass, still more preferably 1 to 15% by mass, based on the total solid content of the composition. is there.

[4] Hydrophobic resin The composition of the present invention may contain a hydrophobic resin.
The hydrophobic resin has at least one of a fluorine atom and a silicon atom.
At least one of a fluorine atom and a silicon atom in the hydrophobic resin may be contained in the main chain of the resin or in a side chain.

  When the hydrophobic resin contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. preferable.

  The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, You may have the substituent of.

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

  Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.

As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom, a group represented by any one of the following general formulas (F2) to (F4) is preferable. However, the present invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (straight or branched). Provided that at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ and at least one of R _{65 to} R ₆₈ are a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. (Preferably having 1 to 4 carbon atoms).

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably a fluoroalkyl group (preferably having 1 to 4 carbon atoms), more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. When R ₆₂ and _{R 63} is a perfluoroalkyl _group, it is preferred that _{R 64} is a hydrogen atom. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

  Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

  Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH _(CF 3) OH and the like, -C _{(CF 3)} 2 OH is preferred.

The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more.
Suitable examples of the repeating unit having a fluorine atom include those shown below.

In the formula, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms and may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.

W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

In addition to these, the hydrophobic resin may have the following units as a repeating unit having a fluorine atom.

In the formula, R _{4 to} R ₇ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms and may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.

However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.

W ₂ represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or alkyl), —NHSO ₂ — or a divalent linking group in which a plurality of these are combined.

  Q represents an alicyclic structure. The alicyclic structure may have a substituent, may be monocyclic, may be polycyclic, and may be bridged in the case of polycyclic. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, norbornyl group, dicyclopentyl group. , Tricyclodecanyl group, tetocyclododecyl 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. Particularly preferred examples of Q include a norbornyl group, a tricyclodecanyl group, a tetocyclododecyl group, and the like.

  The hydrophobic resin may contain a silicon atom.

  The partial structure having a silicon atom preferably has an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.

Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. The divalent linking group includes an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, or a group of two or more groups selected from the group consisting of a ureylene bond. A combination is mentioned.

  n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

  The repeating unit having at least either a fluorine atom or a silicon atom is preferably a (meth) acrylate-based repeating unit.

Hereinafter, although the specific example of the repeating unit which has at least any one of a fluorine atom and a silicon atom is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ , and X ₂ represents —F or —CF ₃ .

  The hydrophobic resin preferably has a repeating unit (b) having at least one group selected from the group consisting of the following (x) to (z).

(X) Alkali-soluble group (y) Group that is decomposed by the action of an alkali developer to increase the solubility in an alkali developer (polar conversion group)
(Z) Decomposition by the action of an acid to increase the solubility in an alkaline developer. Examples of the repeating unit (b) include the following types.

A repeating unit (b ′) having at least one of a fluorine atom and a silicon atom and at least one group selected from the group consisting of the above (x) to (z) on one side chain
A repeating unit (b *) having at least one group selected from the group consisting of (x) to (z) and having no fluorine atom and no silicon atom
A fluorine atom and silicon on one side chain having at least one group selected from the group consisting of (x) to (z) above and on a side chain different from the side chain in the same repeating unit Repeating unit (b ″) having at least one of atoms
It is more preferable that the hydrophobic resin has a repeating unit (b ′) as the repeating unit (b). That is, it is more preferable that the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has at least one of a fluorine atom and a silicon atom.

  When the hydrophobic resin has a repeating unit (b *), a repeating unit having at least one of a fluorine atom and a silicon atom (a repeating unit different from the repeating units (b ′) and (b ″)) In addition, in the repeating unit (b ″), the side chain having at least one group selected from the group consisting of the following (x) to (z), and at least one of a fluorine atom and a silicon atom Are preferably bonded to the same carbon atom in the main chain, that is, in a positional relationship as shown in the following formula (K1).

In the formula, B1 represents a partial structure having at least one group selected from the group consisting of the above (x) to (z), and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

  The group selected from the group consisting of the above (x) to (z) is preferably (x) an alkali-soluble group or (y) a polar conversion group, and more preferably (y) a polar conversion group.

  Examples of the alkali-soluble group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.

  Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

  As the repeating unit (bx) having an alkali-soluble group (x), 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 a linking group is used. Examples include a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be used at the time of polymerization to be introduced at the end of the polymer chain. Either case is preferred.

  In the case where the repeating unit (bx) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, corresponding to the repeating unit (b ′) or (b ″)), the repeating unit (bx) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (bx) is the same as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

The content of the repeating unit (bx) having an alkali-soluble group (x) is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, still more preferably 5 to 20 mol, based on all repeating units in the hydrophobic resin. %.
Specific examples of the repeating unit (bx) having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Examples of the polar conversion group (y) include a lactone group, a carboxylic acid ester group (—COO—), an acid anhydride group (—C (O) OC (O) —), an acid imide group (—NHCONH—), A carboxylic acid thioester group (—COS—), a carbonic acid ester group (—OC (O) O—), a sulfate ester group (—OSO ₂ O—), a sulfonic acid ester group (—SO ₂ O—), and the like. A lactone group is preferred.

  The polarity converting group (y) is, for example, introduced into the side chain of the resin by being included in a repeating unit of acrylic acid ester or methacrylic acid ester, or a polymerization initiator or chain having the polarity converting group (y). Any form in which a transfer agent is introduced at the end of the polymer chain using the polymerization is preferred.

  Specific examples of the repeating unit (by) having a polar conversion group (y) include a repeating unit having a lactone structure represented by formulas (KA-1-1) to (KA-1-17) described later. Can do.

  Further, the repeating unit (by) having the polarity converting group (y) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, the repeating unit (b ′), (b ″) corresponds to the repeating unit (b ′)). The resin having the repeating unit (by) is hydrophobic, but is particularly preferable from the viewpoint of reducing development defects.

As the repeating unit (by), for example, a repeating unit represented by the formula (K0) can be given.

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.

R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.

However, at least one of R _k1 and R _k2 represents a group containing a polarity converting group.

The polar converting group represents a group that decomposes by the action of the alkali developing image solution and increases the solubility in the alkali developing solution as described above. The polar conversion group is preferably a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH—, Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.
Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.

The repeating unit (by) has a group that increases the solubility in a preferable alkali developer by having a group having a partial structure represented by the general formula (KA-1) or (KB-1). Are bonded to each other as in the case of the partial structure represented by the general formula (KA-1) and the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent When it does not have a hand, the group having the partial structure is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the partial structure.

The partial structure represented by the general formula (KA-1) or (KB-1) is linked to the main chain of the hydrophobic resin through a substituent at an arbitrary position.
The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure with the group as X.

X in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, or a carbonic acid ester group. More preferably, it is a carboxylic acid ester group.
The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .

Z _ka1 independently represents a halogen atom, an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group, when there are a plurality of Z _ka1 .
Z _ka1 may be linked to form a ring. Examples of the ring formed by connecting Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).
nka represents an integer of 0 to 10. Preferably it is an integer of 0 to 8, more preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

The electron withdrawing group as Z _{ka1 is the same} as the electron withdrawing group as Y ¹ and Y ² described later. The electron withdrawing group may be substituted with another electron withdrawing group.
Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron withdrawing group, and more preferably an alkyl group, a cycloalkyl group, or an electron withdrawing group. In addition, as an ether group, the thing substituted by the alkyl group or the cycloalkyl group, ie, the alkyl ether group, etc. are preferable. The electron withdrawing group has the same meaning as described above.

Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group as Z _ka1 may have a substituent and may be linear or branched. As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. As a branched alkyl group, Preferably it is C3-C30, More preferably, it is 3-20, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like. C1-C4 things, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, are preferable.

The cycloalkyl group as Z _ka1 may have a substituent, and may be monocyclic or polycyclic. In the case of a polycyclic type, the cycloalkyl group may be a bridged type. That is, in this case, the cycloalkyl group may have a bridged structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable. Examples thereof include a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetocyclododecyl group, and an androstanyl group. As the cycloalkyl group, the following structure is also preferable. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

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

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

  Further, the above group may further have a substituent, and examples of the further substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, and a methoxy group. , Ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, Aralkyl groups such as benzyl group, phenethyl group, cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, the above alkenyl group , Vinyloxy group, propenyloxy group, allyloxy group, buteni May be mentioned an alkenyloxy group such as oxy group, said aryl group, an aryloxy group such as phenoxy group, aryloxycarbonyl group such as benzoyloxy group.

  X in the general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by the general formula (KA-1) is preferably a lactone ring, and more preferably a 5- to 7-membered lactone ring.

In addition, as in the following (KA-1-1) to (KA-1-17), a 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1) has a bicyclo structure, a spiro It is preferred that other ring structures are condensed in a form that forms the structure.
As for the peripheral ring structure to which the ring structure represented by the general formula (KA-1) may be bonded, for example, those in the following (KA-1-1) to (KA-1-17), or The thing according to can be mentioned.

As a structure containing a lactone ring structure represented by the general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. The lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14) and (KA-1-17).

The structure containing the lactone ring structure may or may not have a substituent. Preferable substituents include those similar to the substituent Z _ka1 that the ring structure represented by the general formula (KA-1) may have.

Preferred examples of X in the general formula (KB-1) include a carboxylic acid ester group (—COO—).
Y ¹ and Y ² in formula (KB-1) each independently represent an electron-withdrawing group.
The electron withdrawing group is a partial structure represented by the following formula (EW). * In the formula (EW) represents a bond directly connected to (KA-1) or a bond directly connected to X in (KB-1).

In formula (EW),
n _ew is the repeating number of the linking group represented by —C (R _ew1 ) (R _ew2 ) — and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond, indicating that Y _ew1 is directly bonded.

Y _ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo (cyclo) alkyl group or a haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , an oxy group, a carbonyl group, a sulfonyl group Examples thereof include a group, a sulfinyl group, and a combination thereof. The electron-withdrawing group may have the following structure, for example. The “halo (cyclo) alkyl group” represents an alkyl group and a cycloalkyl group that are at least partially halogenated, and the “haloaryl group” represents an aryl group that is at least partially halogenated. In the following structural formula, R _ew3 and R _ew4 each independently represent an arbitrary structure. R _ew3 and R _ew4 may have any structure, and the partial structure represented by the formula (EW) may have an electron withdrawing property, and may be linked to, for example, the main chain of the resin. An alkyl group and a fluorinated alkyl group;

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with an arbitrary atom or substituent. At least one group of Y _ew1 , R _ew1 , and R _ew2 may be connected to the main chain of the hydrophobic resin through a further substituent.
Y _ew1 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 .
R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group. Represents a fluoromethyl group.

R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.

R _{f1 to} R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.
Examples of the (halo) alkyl group in R _{f1 to} R _f3 include the alkyl group in Z _ka1 described above and a structure in which this is halogenated.

Examples of the (per) halocycloalkyl group and the (per) haloaryl group in R _{f1 to} R _f3 or in the ring formed by linking R _f2 and R _f3 include, for example, the aforementioned cycloalkyl group in Z _ka1 is a halogen atom. And a perfluoroaryl group represented by -C _(n) F _(n-1) and more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H Can be mentioned. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.

The ring that may be formed by linking at least two of R _ew1 , R _ew2 and Y _ew1 preferably includes a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).

  In the repeating unit (by), a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or a general formula (KA) It may have both a partial structure represented by -1) and a partial structure represented by the general formula (KB-1).

Note that part or all of the partial structure of the general formula (KA-1) may also serve as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group functions as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). There is also a possibility.

In addition, when the repeating unit (by) corresponds to the repeating unit (b *) or the repeating unit (b ″) and has a partial structure represented by the general formula (KA-1), the general formula (KA) As for the partial structure represented by -1), it is more preferable that the polarity conversion group is a partial structure represented by -COO- in the structure represented by Formula (KA-1).
The repeating unit (by) can be a repeating unit having the partial structure shown below.

In general formula (bb),
Z ₁ represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Z _{1 s} , they may be the same as or different from each other. Z ₁ preferably represents an ester bond.

Z ₂ represents an alkylene group or a cycloalkylene group, and when a plurality of Z ₂ are present, they may be the same as or different from each other. Z ₂ preferably represents an alkylene group having 1 or 2 carbon atoms or a cycloalkylene group having 5 to 10 carbon atoms.

Ta independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group, or an electron withdrawing group (as Y ¹ and Y ² in the general formula (KB-1)). And preferably represents an alkyl group, a cycloalkyl group, or an electron withdrawing group, and more preferably represents an electron withdrawing group. When there are a plurality of Tas, Tas may be bonded to form a ring.

L ₀ represents a single bond or an m + 1 valent hydrocarbon group (preferably having 20 or less carbon atoms), and preferably represents a single bond. The single bond as L ₀ is when m is 1. The m + 1 valent hydrocarbon group as L ₀ represents, for example, an m + 1 valent hydrocarbon group obtained by removing m-1 arbitrary hydrogen atoms from an alkylene group, a cycloalkylene group, a phenylene group, or a combination thereof. .
L each independently represents a carbonyl group, a carbonyloxy group or an ether group.

Tc is a hydrogen atom, an alkyl group, a cycloalkyl group, a nitrile group, a hydroxyl group, an amide group, an aryl group or an electron withdrawing group (electron withdrawing as Y ¹ and Y ² in the general formula (KB-1)) It is synonymous with a sex group.

  * Represents a bond to the main chain or side chain of the resin. That is, the partial structure represented by the formula (bb) may be directly bonded to the main chain, or the partial structure represented by the formula (bb) may be bonded to the side chain of the resin. The bond to the main chain is a bond to an atom existing in the bond constituting the main chain, and the bond to the side chain is an atom existing outside the bond constituting the main chain. Is a bond to the hand.

m represents an integer of 1 to 28, preferably an integer of 1 to 3, and more preferably 1.
k represents an integer of 0 to 2, and is preferably 1.
q shows the repeating number of group (Z2-Z1), represents the integer of 0-5, Preferably it is 0-2.
r represents an integer of 0 to 5.
In addition, in place of-(L) r-Tc, the -L _0- (Ta) m may be substituted.

  When a fluorine atom or a group containing a fluorine atom is substituted at a position farthest from the above * in the lactone structure represented by the general formula (bb) (position where the number of intervening atoms is maximum), or A case where a fluorine atom is present on a side chain different from the side chain on the lactone side represented by the general formula (bb) in the same repeating unit (corresponding to the above-mentioned repeating unit (b ″)) is also preferable.

The alkylene group as Z ₂ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 in the case of a linear alkylene group, and preferably 3 to 30 carbon atoms, more preferably 3 in the case of a branched alkylene group. ~ 20. Specific examples of the alkylene group as R ₂ include a group obtained by removing one arbitrary hydrogen atom from the above-described specific examples of the alkyl group as Zka1.

The cycloalkylene group as Z ₂ preferably has 3 to 8 carbon atoms, and specific examples thereof include a group in which one arbitrary hydrogen atom has been removed from the cycloalkyl group as Z _ka1 described above. .

  Preferred carbon numbers and specific examples of the alkyl group and cycloalkyl group as Ta and Tc are the same as those described above for the alkyl group and cycloalkyl group as Zka1.

  The alkoxy group as Ta preferably has 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  The aryl group as Ta and Tc is preferably an aryl group having 6 to 12 carbon atoms, such as a phenyl group and a naphthyl group.

The preferred carbon number of the alkylene group and cycloalkylene group as L ₀ and specific examples thereof are the same as those described for the chain alkylene group and cyclic alkylene group as Z ₂ .
As a more specific structure of the repeating unit (bb), a repeating unit having the partial structure shown below is preferable.

In general formulas (ba-2) and (bb-2),
n represents an integer of 0 to 11, preferably an integer of 0 to 5, more preferably 1 or 2.

  p represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 1 or 2.

Tb is independently an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group, or an electron withdrawing group (as Y ¹ and Y ² in the general formula (KB-1)). It is synonymous with an electron withdrawing group, and preferably represents an alkyl group, a cycloalkyl group, or an electron withdrawing group. When there are a plurality of Tb, Tb may be bonded to form a ring.

  * Represents a bond to the main chain or side chain of the resin. That is, the partial structure represented by the formula (ba-2) or (bb-2) may be directly connected to the main chain, or the side chain of the resin may have the formula (ba-2) or (bb-2) The partial structure represented by may be combined.

Z ₁ , Z ₂ , Ta, Tc, L, *, m, q, and r are the same as those in the general formula (bb), and preferable ones are also the same.
The repeating unit (by) can be a repeating unit having a partial structure represented by the general formula (KY-0).

In the general formula (KY-0),
R ₂ represents an alkylene group or a cycloalkylene group, and when there are a plurality of R ₂ groups, they may be the same or different.
R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbons are substituted with fluorine atoms.

R ₄ is a halogen atom, cyano group, hydroxy group, amide group, alkyl group, cycloalkyl group, alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). If R ₄ is a plurality may be the same or different, and two or more R ₄ are attached, may form a ring.

X represents an alkylene group, a cycloalkylene group, an oxygen atom or a sulfur atom.
Z and Za represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of them, they may be the same or different.

* Represents a bond to the main chain or side chain of the resin.
o is the number of substituents and represents an integer of 1 to 7.
m is the number of substituents and represents an integer of 0 to 7.
n represents the number of repetitions and represents an integer of 0 to 5.

The structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) ₁ —COO— (l represents an integer of 1 to 5).
The preferred carbon number range and specific examples of the alkylene group or cycloalkylene group as R ₂ are the same as those described for the alkylene group or cycloalkylene group in Z ₂ of formula (bb).

The linear, branched or cyclic hydrocarbon group as R ₃ has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and preferably 3 carbon atoms when branched. -30, more preferably 3-20, and in the case of a ring, it is 6-20. Specific examples of R ₃ include specific examples of the alkyl group and cycloalkyl group as Z _ka1 described above.

Preferred carbon numbers and specific examples of the alkyl group and cycloalkyl group as R ₄ and R are the same as those described in the alkyl group and cycloalkyl group as Z _ka1 described above.

The acyl group as R ₄ is preferably one having 1 to 6 carbon atoms, and examples thereof include a formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, and pivaloyl group.

Examples of the alkyl moiety in the alkoxy group and alkoxycarbonyl group as R ₄ include a linear, branched or cyclic alkyl moiety, and the preferred carbon number of the alkyl moiety and specific examples thereof are those described above for Z _ka1. The same as those described in the alkyl group and cycloalkyl group.

Preferable carbon number of the alkylene group or cycloalkylene group as X and specific examples thereof are the same as those described for the alkylene group or cycloalkylene group as R ₂ .
Moreover, the repeating unit which has a partial structure shown below as a specific structure of a repeating unit (by) is mentioned.

In general formulas (rf-1) and (rf-2),
X ′ represents an electron-withdrawing substituent, preferably a carbonyloxy group, an oxycarbonyl group, an alkylene group substituted with a fluorine atom, or a cycloalkylene group substituted with a fluorine atom.

  A represents a single bond or a divalent linking group represented by -C (Rx) (Ry)-. Here, Rx and Ry are each independently a hydrogen atom, a fluorine atom, an alkyl group (preferably having 1 to 6 carbon atoms and optionally substituted with a fluorine atom or the like), or a cycloalkyl group (preferably a carbon atom). And may be substituted with a fluorine atom or the like. Rx and Ry are preferably a hydrogen atom, an alkyl group, or an alkyl group substituted with a fluorine atom.

X represents an electron withdrawing group, and specific examples thereof include the above-mentioned electron withdrawing groups as Y ¹ and Y ² , preferably a fluorinated alkyl group or a fluorinated cycloalkyl group. An aryl group substituted with a fluorine or fluorinated alkyl group, an aralkyl group substituted with a fluorine or fluorinated alkyl group, a cyano group, or a nitro group.

  * Represents a bond to the main chain or side chain of the resin. That is, it represents a bond that is bonded to the main chain of the resin through a single bond or a linking group.

  In addition, when X 'is a carbonyloxy group or an oxycarbonyl group, A is not a single bond.

  When the polarity conversion group is decomposed by the action of an alkali developer and converted in polarity, the receding contact angle with water of the resin composition film after alkali development can be lowered. It is preferable from the viewpoint of suppressing development defects that the receding contact angle with water of the film after alkali development is lowered.

  The receding contact angle with water of the resin composition film after alkali development is preferably 50 ° or less, more preferably 40 ° or less, and still more preferably 35 ° at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%. Hereinafter, it is most preferably 30 ° or less.

  The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.

  The receding contact angle of the film after alkali development is a contact angle when the film shown below is measured by the expansion / contraction method described in the examples described later. That is, an organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) is applied on a silicon wafer (8-inch diameter) and baked at 205 ° C. for 60 seconds. The composition is applied and baked at 120 ° C. for 60 seconds to form a film having a thickness of 120 nm. This contact angle is determined by the expansion / contraction method for a film obtained by developing this film with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying.

  The hydrolysis rate of the hydrophobic resin with respect to the alkaline developer is preferably 0.001 nm / second or more, more preferably 0.01 nm / second or more, further preferably 0.1 nm / second or more, Most preferably, it is 1 nm / second or more.

  Here, the hydrolysis rate of the hydrophobic resin with respect to the alkaline developer was 23 ° C. when TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%) was used to form the resin film with only the hydrophobic resin. This is the rate at which the film thickness decreases.

  The repeating unit (by) is more preferably a repeating unit having at least two or more polar conversion groups.

When the repeating unit (by) has at least two polar conversion groups, the repeating unit (by) preferably has a group having a partial structure having two polar conversion groups represented by the following general formula (KY-1). Note that when the structure represented by the general formula (KY-1) does not have a bond, it is a group having a monovalent or higher valent group in which at least one arbitrary hydrogen atom in the structure is removed.

In general formula (KY-1),
R _ky1 and R _ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and R _ky4 are bonded to the same oxygen atom to form a part of a carbonyl group (═O). May be formed.

R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include the same groups as those described above for Y ₁ and Y ₂ in the formula (KB-1), and preferably a halogen atom or the aforementioned —C (R _f1 ) (R _f2 ) —R _f3. A halo (cyclo) alkyl group or a haloaryl group represented by the formula: Preferably _{R ky3} halogen atom, or the _{-C (R f1)} (R f2) is represented by the halo (cyclo) alkyl groups or haloaryl groups _{-R f3,} lactone _{R ky2} is linked to _{R ky1} An electron withdrawing group that forms a ring or has no halogen atom.

R _ky1 , R _ky2 , and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.
Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka1 in formula (KA-1).

As the lactone ring formed by linking R _ky1 and R _ky2 , the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ₁ and Y ₂ in the formula (KB-1).

The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2). Note that the structure represented by the general formula (KY-2) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.

Two or more of R _{ky6 to} R _ky10 may be connected to each other to form a monocyclic or polycyclic structure.

R _ky5 represents an electron withdrawing group. Examples of the electron withdrawing group include the same groups as those described above for Y ₁ and Y ₂ , and preferably a halogen atom or a halo (cyclo (cyclo) represented by —C (R _f1 ) (R _f2 ) —R _f3. ) An alkyl group or a haloaryl group.

Specific examples of R _{ky5 to} R _ky10 include the same groups as Z _ka1 in formula (KA-1).

The structure represented by the formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).

In formula (KY-3), Z _ka1 and nka have the same meanings as those in formula (KA-1). R _ky5 has the same _{meaning as} in formula (KY-2).

L _ky represents an alkylene group, a cycloalkylene group, an oxygen atom or a sulfur atom. _Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

  The repeating unit (b) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation, etc., but is a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Preferably there is. Examples include acrylate-based repeating units (including those having substituents at the α-position and β-position), styrene-based repeating units (including those having substituents at the α-position and β-position), vinyl ether-based repeating units, norbornene-based Repeating units, maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), and the like, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units Preferred are acrylate repeat units, vinyl ether repeat units, and norbornene repeat units, with acrylate repeat units being most preferred.

  When the repeating unit (by) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit (by) corresponds to the repeating unit (b ′) or (b ″)), the repeating unit (by) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

  The content of the repeating unit (by) in the hydrophobic resin is preferably 10 to 100 mol%, more preferably 20 to 99 mol%, still more preferably 30 to 97 mol%, based on all repeating units in the hydrophobic resin. Most preferably, it is 40-95 mol%.

Specific examples of the repeating unit (by) having a group capable of increasing the solubility in an alkali developer are shown below, but are not limited thereto. Moreover, what was mentioned as a specific example of the repeating unit (A) and (C) of the said resin (P) can also be mentioned as a specific example of a repeating unit (by).
Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  In the hydrophobic resin, examples of the repeating unit (bz) having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group described for the resin (P).

  In the case where the repeating unit (bz) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, corresponding to the repeating unit (b ′) or (b ″)), the repeating unit (bz) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

  In the hydrophobic resin, the content of the repeating unit (bz) having a group (z) that decomposes by the action of an acid is preferably 1 to 80 mol%, more preferably, based on all repeating units in the hydrophobic resin. It is 10-80 mol%, More preferably, it is 20-60 mol%.

  Hereinabove, the repeating unit (b) having at least one group selected from the group consisting of (x) to (z) has been described, but the content of the repeating unit (b) in the hydrophobic resin is hydrophobic. It is preferably 1 to 98 mol%, more preferably 3 to 98 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 95 mol% with respect to all repeating units in the conductive resin.

  The content of the repeating unit (b ′) is preferably 1 to 100 mol%, more preferably 3 to 99 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 10 mol% with respect to all repeating units in the hydrophobic resin. 95 mol%.

  The content of the repeating unit (b *) is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, still more preferably 5 to 70 mol%, and most preferably 10 to 10 mol% with respect to all repeating units in the hydrophobic resin. 60 mol%. The content of the repeating unit having at least one of a fluorine atom and a silicon atom used together with the repeating unit (b *) is preferably 10 to 99 mol%, more preferably 20 with respect to all repeating units in the hydrophobic resin. It is -97 mol%, More preferably, it is 30-95 mol%, Most preferably, it is 40-90 mol%.

The content of the repeating unit (b ″) is preferably from 1 to 100 mol%, more preferably from 3 to 99 mol%, still more preferably from 5 to 97 mol%, and most preferably from 10 to 100 mol%, based on all repeating units in the hydrophobic resin. 95 mol%.
The hydrophobic resin may further have a repeating unit represented by the following general formula (III).

In general formula (III):
R _c31 represents a hydrogen atom, an alkyl group, or an alkyl group _optionally substituted with fluorine, a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a fluorine atom, a group containing a silicon atom, or the like.

L _c3 represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.

  The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.

  The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

  The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

  The aryl group is preferably a phenyl group or naphthyl group having 6 to 20 carbon atoms, and these may have a substituent.

R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.

The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).

It is also preferable that the hydrophobic resin further has a repeating unit represented by the following general formula (BII-AB).

In the formula (BII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure with two bonded carbon atoms (C—C).

  When each group in the repeating unit represented by the general formula (III) or (BII-AB) is substituted with a group containing a fluorine atom or a silicon atom, the repeating unit includes at least the fluorine atom and the silicon atom. It corresponds also to the repeating unit which has either.

Specific examples of the repeating unit represented by the general formulas (III) and (BII-AB) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN. Note that the repeating unit in the case where Ra is CF ₃ also corresponds to the repeating unit having at least one of the fluorine atom and the silicon atom.

  As in the case of the resin (P), the hydrophobic resin is naturally low in impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably 0 to 0% by mass. 5 mass% and 0-1 mass% are still more preferable. Thereby, a composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

  As the hydrophobic resin, various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.

  The reaction solvent, polymerization initiator, reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (P).

Specific examples of the hydrophobic resin are shown below. The table below shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), weight average molecular weight, and degree of dispersion.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is formed from an actinic ray-sensitive or radiation-sensitive resin composition by containing a hydrophobic resin containing at least one of a fluorine atom and a silicon atom. When the hydrophobic resin is unevenly distributed on the surface layer of the formed film and the immersion medium is water, the receding contact angle of the film surface with respect to water can be improved, and the immersion water followability can be improved.

  After baking the coating film comprising the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and before exposure, the receding contact angle of the film is the temperature at the time of exposure, usually room temperature 23 ± 3 ° C., humidity 45 ± 5%. 60 ° to 90 °, more preferably 65 ° or more, still more preferably 70 ° or more, and particularly preferably 75 ° or more.

  The hydrophobic resin is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule and contributes to uniform mixing of polar / nonpolar substances. It is not necessary.

  In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with the composition film is important, and there is a demand for the capability of following the high-speed scanning of the exposure head without remaining droplets.

  Hydrophobic resins are hydrophobic, so that development residues (scum) and BLOB defects are likely to deteriorate after alkali development, but they have three or more polymer chains via at least one branch, compared to linear resins. Further, since the alkali dissolution rate is improved, development residue (scum) and BLO defect performance are improved.

  When the hydrophobic resin has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the molecular weight of the hydrophobic resin. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% with respect to all the repeating units in hydrophobic resin, and it is more preferable that it is 30-100 mass%.

  When the hydrophobic resin has silicon atoms, the content of silicon atoms is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the molecular weight of the hydrophobic resin. Moreover, it is preferable that the repeating unit containing a silicon atom is 10-90 mass% with respect to all the repeating units of hydrophobic resin, and it is more preferable that it is 20-80 mass%.

  The weight average molecular weight of the hydrophobic resin is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 30,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: tetrahydrofuran (THF)).

Hydrophobic resins can be used alone or in combination of two or more.
The content of the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive resin composition can be appropriately adjusted and used so that the receding contact angle of the actinic ray or radiation-sensitive resin film falls within the above range. Is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass, based on the total solid content of the light-sensitive or radiation-sensitive resin composition. And particularly preferably 0.5 to 8% by mass.

[6] Other components The composition according to the present invention includes a basic compound, a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, a surfactant, a carboxylic acid onium salt, and a dissolution inhibiting compound. And / or other additives may be further included.

(Basic compound)
The composition according to the present invention may further contain a basic compound. Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (having 6 to 6 carbon atoms). 20). R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each independently represents an alkyl group having 1 to 20 carbon atoms.

  About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable. These alkyl groups are more preferably unsubstituted.

  Preferred basic compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and piperidine. More preferable basic compounds include an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, And aniline derivatives having a hydroxyl group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole.

  Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5, 4,0] Undecar 7-ene.

  Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. More specifically, triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide and 2-oxopropylthiophenium hydroxy Do.

  Examples of the compound having an onium carboxylate structure include a compound having an onium hydroxide structure having a carboxylate as an anion. Examples of the carboxylate include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate.

Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
Examples of aniline compounds include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, and N, N-dihexylaniline.

Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine.
Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

In these compounds, it is preferable that at least one alkyl group is bonded to a nitrogen atom. Further, it is more preferable that an oxygen atom is contained in the chain of the alkyl group to form an oxyalkylene group. The number of oxyalkylene groups is preferably one or more in the molecule, more preferably 3 to 9, and still more preferably 4 to 6. Of these oxyalkylene _{groups, -CH 2 CH 2 O -,} - CH (CH 3) CH 2 O- or _-CH 2 _CH 2 _CH 2 O- by a group represented are especially preferred.

Specific examples of these compounds include compounds (C1-1) to (C3-3) exemplified in [0066] of US2007 / 0224539A.
The total content of the basic compounds is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the composition.

  The molar ratio of the total amount of the acid generator to the total amount of the basic compound is preferably 2.5 to 300, more preferably 5.0 to 200, and still more preferably 7.0 to 150. If this molar ratio is too small, sensitivity and / or resolution may be reduced. If this molar ratio is excessively large, pattern thickening may occur between exposure and heating (post-bake).

(Low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid)
The composition of the present invention contains a low molecular compound (hereinafter, also referred to as “low molecular compound (D)” or “compound (D)”) having a nitrogen atom and a group capable of leaving by the action of an acid. can do.

  The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.

The molecular weight of the low molecular weight compound (D) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
As the compound (D), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.
Compound (D) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
R ′ each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.
R ′ is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

The specific structure of such a group is shown below.

A compound (D) can also be comprised by combining arbitrarily the structure represented by the basic compound and general formula (d-1) which are mentioned later.
The compound (D) particularly preferably has a structure represented by the following general formula (A).
The compound (D) may correspond to the basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.

  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, an aralkyl group, or an alkoxyalkyl group. However, in -C (Rb) (Rb) (Rb), when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.
At least two Rb may be bonded 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 hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group and oxo group. , An alkoxy group and a halogen atom may be substituted. The same applies to the alkoxyalkyl group represented by Rb.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra and / or Rb (these alkyl group, cycloalkyl group, aryl group, and aralkyl group are substituted with the above functional group, alkoxy group, or halogen atom). As may be)
For example, a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., a group derived from these alkanes, for example, A group substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group,
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, groups derived from these cycloalkanes, for example, methyl group, ethyl group, n-propyl group, a group substituted with one or more linear or branched alkyl groups such as i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like,
Groups derived from aromatic compounds such as benzene, naphthalene, anthracene, etc., and groups derived from these aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 A group substituted with one or more linear or branched alkyl groups such as -methylpropyl group, 1-methylpropyl group, t-butyl group, and the like;
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 one or more groups derived from an alkyl group or aromatic compound, a group derived from a linear or branched alkane, a group derived from a cycloalkane, a phenyl group, a naphthyl group , A group substituted with one or more groups derived from an aromatic compound such as anthracenyl group or the like, or the above substituent is a hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo And a group substituted with a functional group such as a group.

  Examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) or a derivative thereof formed by bonding of Ra to each other include, for example, 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 And groups substituted with one or more functional groups such as a group, a morpholino group and an oxo group.

A particularly preferred compound (D) in the present invention is specifically shown, but the present invention is not limited thereto.

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. The definition and specific examples of Ra and Rb are the same as those described in the general formula (A).

  In the present invention, (D) the low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid can be used singly or in combination of two or more.

  The composition of the present invention may or may not contain (D) a low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid. The rate is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the composition combined with the following basic compound. It is.

  The ratio of the acid generator and the compound (D) used in the composition is preferably acid generator / [compound (D) + the above basic compound] (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / [compound (D) + basic compound] (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

(Surfactant)
The composition according to the present invention may further contain a surfactant. By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.

As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. Also, F-top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (Dainippon Ink Chemical Co., Ltd.); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (Asahi Glass Co., Ltd.); Troisol S-366 (Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); F-top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or F601 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos) May be used. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to known surfactants as described above, the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

  The polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate and / or (poly (oxyalkylene)) methacrylate. Even if it distributes, block copolymerization may be sufficient.

  Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group. In addition, units having different chain length alkylene in the same chain, such as poly (block connection body of oxyethylene, oxypropylene, and oxyethylene) and poly (block connection body of oxyethylene and oxypropylene) Also good.

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

For example, Megafac F178, F-470, F-473, F-475, F-476 and F-472 (Dainippon Ink Chemical Co., Ltd.) are mentioned as commercially available surfactants. Further, a copolymer of an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate or methacrylate, an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyethylene)) acrylate or methacrylate And a copolymer of (poly (oxypropylene)) acrylate or methacrylate, a copolymer of an acrylate or methacrylate having a C ₈ F ₁₇ group and (poly (oxyalkylene)) acrylate or methacrylate, and C ₈ F ₁₇ And a copolymer of an acrylate or methacrylate having a group and (poly (oxyethylene)) acrylate or methacrylate and (poly (oxypropylene)) acrylate or methacrylate. That.

  Further, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.

One of these surfactants may be used alone, or two or more thereof may be used in combination.
When the composition according to the present invention contains a surfactant, the content is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, based on the total solid content of the composition. More preferably, it is 0.0005-1 mass%.

(Carboxylic acid onium salt)
The composition according to the present invention may further contain a carboxylic acid onium salt. When carboxylic acid onium salt is contained, transparency to light having a wavelength of 220 nm or less is ensured, sensitivity and resolution are further improved, and density dependency and exposure margin are further improved.

  As the carboxylic acid onium salt, an iodonium salt or a sulfonium salt is preferable. As the anion, for example, a linear or branched alkyl having 1 to 30 carbon atoms or a monocyclic or polycyclic cycloalkylcarboxylic acid anion is preferably used. In particular, a carboxylate anion in which some or all of the hydrogen atoms of these alkyl groups or cycloalkyl groups are substituted with fluorine atoms (hereinafter also referred to as fluorine-substituted carboxylate anions) is preferable. Note that an oxygen atom may be contained in the alkyl or cycloalkyl chain.

  Examples of the fluorine-substituted carboxylate anion include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, and 2 , 2-bistrifluoromethylpropionic acid anion.

  When the composition according to the present invention contains a carboxylic acid onium salt, the content thereof is generally 0.1 to 20% by mass, preferably 0.8%, based on the total solid content of the composition. It is 5-10 mass%, More preferably, it is 1-7 mass%.

(Dissolution inhibitor compound)
The composition according to the present invention may further contain a dissolution inhibiting compound. Here, the “dissolution inhibiting compound” is a compound having a molecular weight of 3000 or less, which decomposes by the action of an acid and increases the solubility in an alkaline developer.

  As this dissolution inhibiting compound, since it does not decrease the transmittance for light having a wavelength of 220 nm or less, acid decomposition such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996) An alicyclic or aliphatic compound containing a functional group is preferred. Examples of the acid-decomposable group and the alicyclic structure include the same ones as described above.

  When the composition according to the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, the dissolution inhibiting compound is a compound containing a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. Is preferred. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, and what contains 2-6 pieces is still more preferable.

  When the composition according to the present invention contains a dissolution inhibiting compound, the content is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total solid content of the composition. is there.

Specific examples of the dissolution inhibiting compound are given below.

(Other additives)
If necessary, the composition according to the present invention contains a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or An alicyclic or aliphatic compound containing a carboxy group may further be included.

  For example, phenol compounds having a molecular weight of 1000 or less can be easily obtained with reference to the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. Can be synthesized.

  Examples of alicyclic or aliphatic compounds containing a carboxy group include carboxylic acid derivatives containing a steroid structure such as cholic acid, deoxycholic acid and lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, And cyclohexanedicarboxylic acid.

<Pattern formation method>
When forming a film | membrane using the composition which concerns on this invention, it is preferable that the film thickness of this film | membrane is 30-250 nm, and it is more preferable that it is 30-200 nm. In this way, the resolution can be further improved. A film having such a film thickness can be formed by adjusting the viscosity by setting the solid content concentration in the composition to an appropriate range and improving the coating property and film forming property.

  The total solid content concentration in the composition is preferably 3.5 to 8% by mass, and more preferably 3.5 to 5% by mass.

  The composition according to the present invention is typically used as follows. That is, each of the above components is dissolved in a predetermined solvent (preferably the above mixed solvent), and the obtained solution is filtered and applied onto a predetermined support. The pore size of the filter used for filter filtration is 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. This filter is preferably made of polytetrafluoroethylene, polyethylene or nylon.

  This composition is applied to a substrate (eg, silicon / silicon dioxide coating, silicon nitride and chromium-deposited quartz substrate, etc.) used for the manufacture of precision integrated circuit elements using a spinner and a coater. Is done. Thereafter, this is dried to form an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as a photosensitive film). In addition, a known antireflection film can be applied in advance.

  Next, the photosensitive film is irradiated with actinic rays or radiation, preferably baked (heated), and then developed. By performing baking, a more favorable pattern can be obtained.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet (EUV) light, X-rays, and electron beams. Among these, far ultraviolet light having a wavelength of preferably 250 nm or less, more preferably 220 nm or less, particularly preferably 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ Excimer laser (157 nm), EUV light (13 nm), X-ray or electron beam is preferred. In particular, an ArF excimer laser, an F ₂ excimer laser, EUV light, or an electron beam is preferable.

  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.

  Liquid immersion exposure may be performed on the film formed using the composition according to the present invention. That is, irradiation with actinic rays or radiation may be performed in a state where a liquid having a higher refractive index than air is filled between the film and the lens. Thereby, it becomes possible to further improve the resolution.

The immersion liquid used for the immersion exposure will be described below.
The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has the smallest possible temperature coefficient of refractive index so as to minimize distortion of the optical image projected onto the composition film. In particular, when the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
In addition, a medium having a refractive index of 1.5 or more can be used in order to further shorten the wavelength. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, the surface tension of the water is decreased and the surface activity is increased, so that the composition layer on the wafer is not dissolved and the influence on the optical coating on the lower surface of the lens element is ignored. A possible additive (liquid) may be added in a small proportion.

  The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specific examples include methyl alcohol, ethyl alcohol, and isopropyl alcohol. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the concentration of the content changes, the refractive index change of the entire liquid can be made extremely small. On the other hand, when an opaque substance or an impurity having a refractive index significantly different from that of water is mixed with 193 nm light, the optical image projected on the composition is distorted. Therefore, distilled water is preferable as the water to be used. . Further, pure water filtered through an ion exchange filter or the like may be used.

  The electrical resistance of the water used as the immersion liquid is preferably 18.3 MQcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and it is desirable that deaeration treatment is performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for improving the refractive index may be added to water, and heavy water (D ₂ O) may be used instead of water.

  In order to avoid contact between the composition film and the immersion liquid, an immersion liquid poorly soluble film (hereinafter also referred to as “top coat”) may be provided between the composition film and the immersion liquid. Functions necessary for the top coat include suitability for application on the composition layer, transparency to radiation, particularly radiation having a wavelength of 193 nm, and poor immersion liquid solubility. As the top coat, it is preferable to use a top coat that can be uniformly applied on the composition layer without being mixed with the composition.

  From the viewpoint of transparency at 193 nm, the topcoat is preferably a polymer that does not contain aromatics. Examples of such polymers include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, and fluorine-containing polymers. The hydrophobic resin described above is also suitable as a top coat. When impurities are eluted from the top coat into the immersion liquid, the optical lens is contaminated. Therefore, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

  When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the composition is preferable. In terms that the peeling step can be performed simultaneously with the development processing step of the composition, it is preferable that the peeling step can be performed with an alkali developer. The top coat is preferably acidic from the viewpoint of peeling with an alkaline developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the composition.

  There is preferably no or small difference in refractive index between the top coat and the immersion liquid. In this case, the resolution can be improved. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water as the immersion liquid. Therefore, the top coat for ArF immersion exposure is close to the refractive index of water (1.44). preferable.

  Moreover, it is preferable that a topcoat is a thin film from a viewpoint of transparency and a refractive index. The top coat is preferably not mixed with the composition film and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Further, when the immersion liquid is an organic solvent, the top coat may be water-soluble or water-insoluble.

  As the alkaline developer in the development step, an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but an inorganic alkali, primary amine, secondary amine, tertiary amine, alcohol amine, and cyclic amine are used. Other alkaline aqueous solutions such as amines can also be used. An appropriate amount of alcohols and / 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 can be used, and an appropriate amount of a surfactant can be added. Moreover, you may perform the process which removes the developing solution or rinse liquid adhering on a pattern with a supercritical fluid after a development process or a rinse process.

<Synthesis Example 1: Synthesis of monomer (1)>
Monomer (1) was synthesized according to the following scheme.

  First, compound (1) was synthesized by the method described in International Publication No. 07/037213 pamphlet. Next, 150.00 parts by mass of water was added to 35.00 parts by mass of the compound (1), and then 27.30 parts by mass of NaOH was further added. The resulting reaction solution was stirred for 9 hours under heating and refluxing conditions. Hydrochloric acid was added to make it acidic, and the product was extracted with ethyl acetate. The organic layers were combined and concentrated to obtain 36.90 parts by mass of compound (2) (yield 93%).

  To 50.87 parts by mass of compound (2), 300 parts by mass of ethyl acetate was added. Thereafter, 51.76 parts by mass of 1,1,1,3,3,3-hexafluoroisopropyl alcohol and 3.18 parts by mass of 4-dimethylaminopyridine were added and stirred. 54.20 parts by mass of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added to the resulting solution, and the mixture was stirred for 5 hours. The reaction solution was added to 200 mL of 1N hydrochloric acid to stop the reaction. The organic layer was separated, washed with 1N hydrochloric acid, further washed with water, and the organic layer was concentrated. Subsequently, 67.60 mass parts of compound (3) was obtained by azeotropic dehydration of water using toluene (yield 76%).

  15.00 parts by mass of the compound (3) was dissolved in 67.5 parts by mass of deaerated acetonitrile, and after bubbling with nitrogen gas, the reaction solution was cooled to 10 ° C. or lower. Next, while maintaining the liquid temperature at 10 ° C. or lower, 8.11 parts by mass of methacrylic acid chloride was added, and 7.85 parts by mass of triethylamine was added dropwise. Thereafter, the reaction solution was further stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was added to a solution in which 9.0 parts by mass of concentrated hydrochloric acid was diluted with 675 parts by mass of water and cooled to 5 ° C. After stirring for 30 minutes, the deposited precipitate was collected by filtration and washed with water. The obtained powder was dissolved in 45.6 parts by mass of acetonitrile, and the obtained solution was dropped into 304.0 parts by mass of water cooled to 5 ° C. After stirring for 30 minutes, the deposited precipitate was collected by filtration and washed with water. 76.1 parts by mass of heptane was added to the obtained powder and stirred at room temperature for 1 hour. The solid was collected by filtration and dried to obtain 13.7 parts by mass of compound (4) (yield 77%).

  5.00 parts by mass of the compound (4) was dissolved in 50 parts by mass of tetrahydrofuran. 50 parts by mass of water and 2.16 parts by mass of potassium carbonate were added to the resulting solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, concentrated hydrochloric acid was added to adjust the pH of the reaction solution to 1 or less. To this, 100 parts by mass of ethyl acetate was added to extract the product. The separated organic layer was washed with 50 parts by mass of 1N hydrochloric acid, and the organic layer was concentrated to obtain 3.01 parts by mass of compound (5) (yield 94%).

0.13 parts by mass of dimethylformamide and 2.00 parts by mass of thionyl chloride were added to 2.00 parts by mass of the compound (5). The reaction solution was heated to 75 ° C. and stirred for 1 hour. After completion of the reaction, unreacted thionyl chloride was removed under reduced pressure. This obtained compound (6).
Subsequently, the compound (7) was synthesized by the method described in Journal of Medicinal Chemistry, 1975, Vol. 18, No. 11, 1065-1070. 0.86 parts by mass of the compound (7) was dissolved in 4.0 parts by mass of acetonitrile. To the obtained solution, 0.84 parts by mass of triethylamine and 0.28 parts by mass of 4-dimethylaminopyridine were added. The reaction solution was cooled to 10 ° C. or lower and stirred. While maintaining the liquid temperature at 10 ° C. or lower, a solution prepared by dissolving previously synthesized compound (6) in 3.5 parts by mass of acetonitrile was added dropwise. After completion of the reaction, 50 parts by mass of ethyl acetate and 25 parts by mass of sodium hydrogen carbonate aqueous solution were added to extract the product. The separated organic layer was washed with saturated aqueous sodium hydrogen carbonate, and then further washed with water. The organic layer was concentrated, and the concentrate was purified by column chromatography to obtain 0.54 parts by mass of monomer (1) (yield 21%).

¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 0.83-1.00 (3H), 1.63-1.77 (8H), 1.85-2.15 (8H), 2.18-2.56 (1H), 2.64 (1H), 3.55-3.56 (1H), 4.63 (1H), 4.69-4.71 (1H), 5.67 (1H), 6.10 (1H).

<Synthesis Example 2: Synthesis of monomer (4)>
Monomer (4) was synthesized according to the following scheme.

30.00 parts by mass of tetrahydrofuran was added to 17.09 parts by mass of methyl glycolate [Compound (10); manufactured by TCI]. To this, 21.15 parts by mass of triethylamine was added and cooled to 0 ° C., and then 20.85 parts by mass of methacrylic acid chloride was added dropwise. After returning to room temperature, the mixture was stirred for 2 hours. After adding aqueous sodium hydrogen carbonate solution, the product was extracted with ethyl acetate. The organic layers were combined, MgSO ₄ was added and filtered, and the filtrate was concentrated to obtain 28.51 parts by mass of compound (11) (yield 95%).

180 mL of acetone was added to 28.5 parts by mass of compound (11), cooled to 0 ° C., and 180 parts by mass of 1N aqueous sodium hydroxide solution was added dropwise. The mixture was stirred for 30 minutes, acidified with hydrochloric acid, and extracted with ethyl acetate. The organic layers were combined, MgSO ₄ was added, the mixture was filtered, and the filtrate was concentrated to obtain 21.2 parts by mass of compound (12) (yield 82%).

  To 15.00 parts by mass of the compound (12), 300 parts by mass of toluene was added. 7.00 parts by mass of the compound (3) and 3.80 parts by mass of p-toluenesulfonic acid monohydrate were added thereto, and the resulting water was refluxed for 6 hours while removing water by azeotropy. did. The reaction solution was concentrated, and the concentrate was purified by column chromatography to obtain 13.52 parts by mass of compound (13) (yield 71%).

  Thereafter, monomer (4) was synthesized in the same manner as described in Synthesis Example 1 except that compound (13) was used instead of compound (4) (yield 18%).

<Synthesis Example 3: Synthesis of monomer (7)>
Monomer (7) was synthesized according to the following scheme.

  20.00 parts by mass of cyclohexyl vinyl ether (manufactured by TCI) was cooled to 10 ° C. or lower. While maintaining the liquid temperature at 10 ° C. or lower, 4.26 parts by mass of Compound (5) was added. After returning to room temperature, the mixture was stirred for 1 hour. After completion of the reaction, unreacted cyclohexyl vinyl ether was removed under reduced pressure. The obtained crude product was purified by column chromatography to obtain 1.32 parts by mass of monomer (7) (yield 21%).

<Synthesis Example 4: Synthesis of Monomer (8)>
Monomer (8) was synthesized according to the following scheme.

The compound (18) was synthesized by the method described in Journal of the Chemical Society, 1925, 127, 475. A monomer (8) was synthesized in the same manner as described in Synthesis Example 1 except that the compound (18) was used instead of the compound (2) (yield 11%).
In addition, other monomers corresponding to the repeating unit (A) were synthesized in the same manner as in Synthesis Examples 1 to 4 described above.

<Synthesis Example 5: Synthesis of Polymer (1)>

  Under a nitrogen stream, 7.12 parts by mass of PGMEA / PGME mixed solvent (mass ratio: 8/2) was placed in a three-necked flask and heated to 85 ° C. In this solvent, the above monomers were added in the order of 3.16 parts by mass, 0.54 parts by mass, 1.04 parts by mass, 1.96 parts by mass, and 0.344 parts by mass (0.65 mol% based on the monomers). ) 2,2′-azobisisobutyric acid dimethyl [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] was dissolved in 3.2 parts by mass of a PGMEA / PGME mixed solvent (mass ratio: 8/2). The solution was added dropwise over 6 hours. After completion of dropping, the reaction was further continued at 85 ° C. for 2 hours. After allowing the reaction solution to cool, it was dropped into a mixed solution of 140 parts by mass of heptane and 60 parts by mass of ethyl acetate over 20 minutes to precipitate a powder. The precipitated powder was collected by filtration and dried to obtain 4.6 parts by mass of polymer (1). The weight average molecular weight by GPC method of the obtained polymer (1) was 8260 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.50.

The following polymers (2) to (26) were synthesized in the same manner as the polymer (1). 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.

<ArF dry exposure>
(Resist preparation)
The components shown in Table 4 below were dissolved in the solvents shown in the same table to prepare solutions. Thereafter, the obtained solution was filtered using a polyethylene filter having a pore size of 0.1 μm to prepare a positive resist solution.

(Resist evaluation)
An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied on an 8 inch silicon wafer and baked at 205 ° C. for 60 seconds. Thereby, an antireflection film having a film thickness of 78 nm was formed on the silicon wafer. On top of this, the above positive resist solution was applied and baked at 90 ° C. for 60 seconds. Thereby, a resist film having a thickness of 150 nm was formed.
The obtained resist film was subjected to pattern exposure using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75). As the reticle, a 6% halftone mask having a line size = 75 nm and a line: space = 1: 1 was used. Subsequently, it heated at 95 degreeC for 60 second, and used for the development process for 30 second using 2.38 mass% tetramethylammonium hydroxide aqueous solution. Thereafter, the substrate was rinsed with pure water, spin-dried, and then heated at 90 ° C. for 90 seconds to obtain a resist pattern.

[Coating defects]
The photosensitive resin composition is applied onto an 8-inch silicon substrate that has been subjected to hexamethyldisilazane treatment by a spin coater, and heated and dried on a hot plate at 90 ° C. for 60 seconds to form a resist film having a thickness of 150 nm. did. The number of defects of this resist film was measured using a KLA2360 machine (manufactured by KLA Tencor). At this time, the number of defects in Comparative Example 1 was normalized to 1 and represented. The smaller the value, the better the defect performance.
[Coating film thickness uniformity]
The photosensitive resin composition was applied onto an 8-inch silicon substrate subjected to hexamethyldisilazane treatment by a spin coater, heated and dried on a hot plate at 90 ° C. for 60 seconds, and a film thickness of 120 nm (5 in wafer surface). An average value of the portions) was formed. The resist film thickness was measured at 29 locations on the wafer surface using a film thickness meter (VM-3110: Dainippon Screen Co., Ltd.), and the dispersion (3σ) of the variation was used as an index.

[PEB temperature dependence]
An exposure amount that reproduces a line and space 1/1 with a mask size of 75 nm is set as an optimal exposure amount, and after performing exposure at the optimal exposure amount, + 2 ° C and -2 ° C (93 ° C, 97 ° C.) was subjected to post-heating, and the obtained line and space was measured, and their line widths L ₁ and L ₂ were determined. The PEB temperature dependency was defined as the fluctuation of the line width per PEB temperature change of 1 ° C., and was calculated by the following formula.
PEB temperature dependency (nm / ° C.) = | L ₁ −L ₂ | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.
Table 4 below shows the evaluation results.

  Abbreviations in Table 4 are as follows. These abbreviations are also common to the examples described later.

(Acid generator)

(Basic compound)
DIA: 2,6-diisopropylaniline TBAH: tetrabutylammonium hydroxide TMEA: tris (methoxyethoxyethyl) amine PEA: N-phenyldiethanolamine TOA: trioctylamine PBI: 2-phenylbenzimidazole DHA: N, N-dihexylaniline TEA: Triethanolamine DBA: N, N-dibutylaniline

(Surfactant)
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd .; fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd .; fluorine and silicon)
W-3: Troisol S-366 (manufactured by Troy Chemical Co .; fluorine type)
W-4: PF656 (manufactured by OMNOVA; fluorine-based)
W-5: PF6320 (manufactured by OMNOVA; fluorine-based).

(solvent)
A1: Propylene glycol monomethyl ether A2: Butyl acetate A3: Methyl pyruvate A4: Ethyl lactate B1: γ-butyrolactone B2: Propylene carbonate C1: Propylene glycol monomethyl ether acetate D1: Cyclohexanone (dissolution inhibitor compound)
D-1: t-butyl lithocholic acid.

<ArF immersion exposure>
(Resist preparation)
The components shown in Table 5 below were dissolved in the solvents shown in the same table to prepare solutions. Thereafter, the obtained solution was filtered using a polyethylene filter having a pore size of 0.1 μm to prepare a positive resist solution.

(Resist evaluation)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on a 12 inch silicon wafer and baked at 205 ° C. for 60 seconds. As a result, an antireflection film having a film thickness of 98 nm was formed on the silicon wafer. On top of this, the above positive resist solution was applied and baked at 90 ° C. for 60 seconds. Thereby, a resist film having a thickness of 150 nm was formed.

The resulting resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (XT1700i, NA1.20, C-Quad, outer sigma 0.960, inner sigma 0.709, XY deflection manufactured by ASML). As the reticle, a 6% halftone mask having a line size = 60 nm and a line: space = 1: 1 was used. Moreover, ultrapure water was used as the immersion liquid.
Subsequently, it heated at 95 degreeC for 60 second, and used for the development process for 30 second using 2.38 mass% tetramethylammonium hydroxide aqueous solution. Then, it rinsed using the pure water and spin-dried and obtained the resist pattern.

[Coating defects]
The photosensitive resin composition is applied onto a 12-inch silicon substrate treated with hexamethyldisilazane by a spin coater, and heated and dried on a hot plate at 90 ° C. for 60 seconds to form a resist film having a thickness of 150 nm. did. The number of defects of this resist film was measured using a KLA2360 machine (manufactured by KLA Tencor). At this time, the number of defects in Comparative Example 1 was normalized to 1 and represented. The smaller the value, the better the defect performance.
[Coating film thickness uniformity]
The photosensitive resin composition was applied on a 12-inch silicon substrate subjected to hexamethyldisilazane treatment by a spin coater, heated and dried on a hot plate at 90 ° C. for 60 seconds, and 150 nm (at 5 locations on the wafer surface). An average value) resist film was formed. The resist film thickness was measured at 61 points in the wafer surface using a film thickness meter (VM-3110: Dainippon Screen Co., Ltd.), and the dispersion (3σ) of the variation was used as an index.
A smaller value indicates a better performance change.

[PEB temperature dependence]
An exposure amount that reproduces a line and space 1/1 with a mask size of 60 nm is set as an optimal exposure amount, and after performing exposure at the optimal exposure amount, + 2 ° C and -2 ° C (93 ° C, 97 ° C.) was subjected to post-heating, and the obtained line and space was measured, and their line widths L ₁ and L ₂ were determined. The PEB temperature dependency was defined as the fluctuation of the line width per PEB temperature change of 1 ° C., and was calculated by the following formula.
PEB temperature dependency (nm / ° C.) = | L ₁ −L ₂ | / 4
The smaller the value, the smaller the performance change with respect to the temperature change. These measurement results are shown in Table 5 below.

In addition, in the column of “addition form” in Table 5, the addition form of the hydrophobic resin is described as “addition” or “TC”. In the example described as “addition”, the hydrophobic resin is contained in the resist solution. In the example described as “TC”, a resist film is formed using a resist solution not containing a hydrophobic resin, and then a top coat (TC) protective film containing a hydrophobic resin is provided on the upper layer.
When the addition form of the hydrophobic resin was “TC”, the following operation was performed after forming the resist film. The solvents listed in the column of “solvent for TC” are as follows.
S-1: 2-ethylbutanol.

<Formation method of top coat>
The hydrophobic resin shown in Table 5 was dissolved in a solvent, and the resulting solution was applied onto the resist film using a spin coater. Thereafter, this was heated and dried at 115 ° C. for 60 seconds to form a topcoat layer having a thickness of 0.05 μm. After the formation, the application unevenness of the top coat layer was observed to confirm that the top coat layer was uniformly applied.

  The abbreviations for the hydrophobic resins in Table 5 correspond to the formula numbers in the specific examples given above.

Claims (14)

Repeating structure comprising a structural part (S1) that decomposes by the action of an acid to generate an alkali-soluble group and a structural part (S2) that decomposes by the action of an alkali developer and increases the dissolution rate in the alkali developer A resin (P) containing a unit (A), a compound capable of generating an acid upon irradiation with actinic rays or radiation, and an actinic ray-sensitive or radiation-sensitive resin composition containing a solvent. An actinic ray-sensitive or radiation-sensitive resin composition containing at least one of the solvents listed in the groups and Y groups.
(Group X) alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxyacetates, alkyl alkoxypropionates, alkyl pyruvates, alkyl acetates;
(Group Y) Cyclic lactones and alkylene carbonates.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising an alkylene glycol monoalkyl ether carboxylate.   3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein at least one solvent selected from Group X, at least one solvent selected from Group Y, and alkylene glycol mono The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, comprising at least three kinds of solvents with alkyl ether carboxylates.   The actinic ray-sensitive light according to claim 1, wherein the total content of the solvent selected from the X group and the Y group is 92% by mass or more based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Or radiation sensitive resin composition.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein the total content of the solvent is 95% by mass or more based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.   The total content of the solvent selected from the X group and the Y group and the alkylene glycol monoalkyl ether carboxylate is 92% by mass or more based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Item 4. The actinic ray-sensitive or radiation-sensitive resin composition according to Item 2 or 3.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 6, wherein the total content of the solvent is 95% by mass or more based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein the structural site (S2) contains a lactone structure.   The actinic ray-sensitive property according to any one of claims 1 to 8, wherein the structural site (S1) is bonded to at least one of two carbon atoms adjacent to an ester group constituting the lactone structure. Or a radiation sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 9, wherein the repeating unit (A) has a structure represented by the following general formula.

In Formula (1), R ₂ independently represents a chain or cyclic alkylene group when n ≧ 2. R < ₃ > represents an alkyl group or a cycloalkyl group each independently when k> = 2. When k ≧ 2, at least two of R ₃ may be bonded to each other to form a ring. X represents an alkylene group, an oxygen atom, or a sulfur atom. Y represents the structural unit (S1) independently when m ≧ 2. Z each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond when n ≧ 2. k represents an integer of 0 to 5. m represents an integer of 1 to 5 that satisfies the relationship m + k ≦ 6. n represents an integer of 0 to 5.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10, further comprising a hydrophobic resin.   A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1.   A pattern forming method comprising forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, exposing the film, and developing the exposed film. .   The pattern forming method according to claim 13, wherein the exposure is performed through an immersion liquid.