JP2011168698A - Method for producing active light-sensitive resin or radiation-sensitive resin, resin obtained by the method, composition containing the resin, and resist film and method for forming pattern by using the composition, - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technology enabling the production of an active light-sensitive or a radiation-sensitive resin containing a recurring unit including a structural part decomposed by the irradiation of the active light or radiation to produce an acid, and a recurring unit including a group decomposed by the acid to produce an alkali-dissolvable group, in a high purity. <P>SOLUTION: This method for producing the active light-sensitive or radiation-sensitive resin is provided by comprising the polymerization of a reaction system containing a first monomer including the structural part generating the acid by the decomposition with the irradiation of the active light or radiation and a second monomer including the group decomposed by the action of the acid to form the alkali-dissolvable group, in the presence of a basic compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an actinic ray-sensitive or radiation-sensitive resin, a resin obtained by this method, a composition containing this resin, a resist film, and a pattern forming method. 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, a resin that can be used as one component of the composition, and a method for producing the resin. More specifically, the present invention relates to a composition suitable when using an ultraviolet ray of 250 nm or less, an electron beam, soft X-rays, etc. as an irradiation source, a resin that can be used as one component of the composition, and production of the resin. Regarding the method.

  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. .

  A chemically amplified resist generates acid in the exposed area by irradiation with radiation such as deep ultraviolet light, and the reaction using this acid as a catalyst changes the solubility of the active radiation irradiated area and non-irradiated area in the developer. A pattern is formed 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.

  On the other hand, in recent years, in addition to lithography using excimer laser light, development using lithography using electron beams, X-rays, soft X-rays, or EUV light is also progressing. In addition, microfabrication using a resist composition is not only directly used for manufacturing an integrated circuit, but also recently applied to production of a so-called imprint mold structure (for example, Patent Documents 1 and 2). And Non-Patent Document 1). Therefore, even when using electron beam, X-ray, soft X-ray or EUV light as an exposure light source, it is important to satisfy high sensitivity, high resolution, good pattern shape and good roughness characteristics at the same time. It is a difficult issue and needs to be resolved.

  Patent Document 3 describes that the pattern shape and line edge roughness (LER) can be improved by using a resin having a photoacid generator in the polymer side chain. However, in the generation that forms the latest pattern with a line width of 45 nm or less to which the immersion process is applied, further improvement in roughness characteristics is required. There is also room for improvement in dry etching resistance.

  Patent Document 4 describes that high sensitivity, high resolution, and good LER can be achieved by using a resin having a photoacid generator in the polymer side chain. However, in the technique described in this document, it is difficult to suppress acid diffusion in the post-exposure heating step (Post Exposure Bake: PEB) because the acid generated by irradiation with radiation is a low molecular weight compound. Therefore, it was difficult to say that the effect of improving LER was sufficient.

  As described above, the performance of the resist composition can be improved by using a resin having a photoacid generator in the polymer side chain. However, sufficient knowledge has not been accumulated about the method for producing such a resin, and it has been difficult to obtain the target resin with high purity.

JP 2004-158287 A JP 2008-162101 A JP 2009-93137 A JP 2006-215526 A

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

  An object of the present invention includes a repeating unit having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid, and a repeating unit having a group that decomposes by the action of an acid to generate an alkali-soluble group. An object of the present invention is to provide a technique capable of producing an actinic ray-sensitive or radiation-sensitive resin with high purity.

  For example, the present invention is as follows.

  [1] A first monomer having a structural part that decomposes upon irradiation with actinic rays or radiation to generate an acid, and a second monomer having a group that decomposes by the action of an acid to generate an alkali-soluble group A method for producing an actinic ray-sensitive or radiation-sensitive resin, which comprises polymerizing a reaction system containing the compound in the presence of a basic compound.

[2] The basic compound is at least one selected from the group consisting of a compound represented by the following general formula (BS-1), a compound having a nitrogen-containing heterocyclic structure, and an ammonium salt [1] The manufacturing method of resin as described in 1 ..

In general formula (BS-1),
Each R independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group (except when all three Rs are hydrogen atoms). At least two of the three Rs may be connected to each other to form a ring.

  [3] The method for producing a resin according to [2], wherein the basic compound is at least one of a compound represented by the general formula (BS-1) and a compound having a nitrogen-containing heterocyclic structure.

  [4] The method for producing a resin according to any one of [1] to [3], wherein an amount of the basic compound used is 0.01 to 200 mol% with respect to the first monomer.

  [5] The resin production according to any one of [1] to [4], wherein the repeating unit corresponding to the first monomer generates an acid anion in a side chain of the resin upon irradiation with the actinic ray or radiation. Method.

[6] The first monomer includes a cation moiety represented by at least one of the following general formulas (ZI-3C) and (ZI-4C): [1] to [5] Resin production method.

In general formula (ZI-3C),
M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group. When M has a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.
R _1c and R _2c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
At least two of M, R _1c and R _2c may be bonded to each other to form a ring.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. R _x and R _y may be bonded to each other to form a ring.
In general formula (ZI-4C),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.
R ₁₄ 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 group when r ≧ 2. Represents a group having a cycloalkyl skeleton.
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.
l represents an integer of 0-2.
r represents an integer of 0 to 8.

  [7] The method for producing a resin according to any one of [1] to [6], wherein the reaction system further includes an aprotic solvent.

  [8] The method for producing a resin according to any one of [1] to [7], further comprising purifying the product obtained by the reaction by reprecipitation.

  [9] The method for producing a resin according to [8], wherein the reprecipitation is repeated twice or more.

  [10] As the poor solvent in the second or more reprecipitation, the organic solvent is used for the first time and the aqueous solvent is used for the second time, or the aqueous solvent is used for the first time and the organic solvent is used for the second time. [9] The method for producing a resin according to [9].

  [11] An actinic ray-sensitive or radiation-sensitive resin obtained by the production method according to any one of [1] to [10].

  [12] An actinic ray-sensitive or radiation-sensitive composition containing the resin according to [11].

  [13] A resist film formed using the composition according to [12].

  [14] A pattern forming method comprising forming a film using the composition according to [12], exposing the film, and developing the exposed film.

  According to the present invention, there is a feeling that includes a repeating unit having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid and a repeating unit having a group that decomposes by the action of an acid to generate an alkali-soluble group. An actinic ray-sensitive or radiation-sensitive resin can be produced with high purity.

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.

  The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains an actinic ray-sensitive or radiation-sensitive resin (P). Hereinafter, the structure of this resin (P) and its manufacturing method are demonstrated in detail.

<Actinic ray sensitive or radiation sensitive resin (P)>
The actinic ray-sensitive or radiation-sensitive resin (P) is composed of a repeating unit (A) having a structural portion that decomposes upon irradiation with actinic rays or radiation to generate an acid, and an alkali-soluble group that decomposes by the action of an acid. And a repeating unit (B) having a group capable of generating

[Repeating unit (A)]
As the repeating unit (A), any repeating unit capable of decomposing upon irradiation with actinic rays or radiation to generate an acid can be used.

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

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

In the general formulas (III) to (V), the alkyl groups represented by R _{04 to} R ₀₅ and R _{07 to} R ₀₉ are preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group that may have a substituent. Group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group and the like, and an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms. .

  Examples of the cycloalkyl group include cycloalkyl groups that may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.
Examples of the alkyl group contained in the alkoxycarbonyl group include R _{04 to} R ₀₅ , R ₀₇ to
The same alkyl group as R ₀₉ is preferable.

As the alkyl group for R _{25 to} R ₂₇ and R ₃₃ , an optionally substituted methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, An alkyl group having 20 or less carbon atoms such as 2-ethylhexyl group, octyl group or dodecyl group is exemplified, and an alkyl group having 8 or less carbon atoms is more preferable.

Examples of the cycloalkyl group include cycloalkyl groups that may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.
Preferred examples of the alkenyl group include those having 2 to 6 carbon atoms, such as a vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, and cyclohexenyl group which may have a substituent. It is done.

As the aryl group, a monocyclic or polycyclic aromatic group having 6 to 14 carbon atoms which may have a substituent is preferable. Specifically, a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, A naphthyl group etc. are mentioned. In addition, aryl groups may be bonded to form a multicycle.
Examples of the aralkyl group include those having 7 to 15 carbon atoms which may have a substituent such as a benzyl group, a phenethyl group, or a cumyl group.
The ring formed by combining R ₂₆ and R ₂₇ together with the nitrogen atom is preferably a ring that forms a 5- to 8-membered ring. Specific examples include pyrrolidine, piperidine, and piperazine.

The arylene group of X _{1 to} X ₃ is preferably an arylene group having 6 to 14 carbon atoms which may have a substituent, and specific examples thereof include a phenylene group, a tolylene group and a naphthylene group.

  The alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.

  Preferred examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.

Preferred substituents for each group in the general formulas (III) to (V) include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, R ₀₄ to R _09, R ₂₅ ~R _27, alkyl groups listed R _33, a methoxy group, an ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, an alkoxy group or a butoxy group, a methoxycarbonyl group, such as ethoxycarbonyl group Examples include acyl groups such as alkoxycarbonyl groups, formyl groups, acetyl groups, and benzoyl groups, acyloxy groups such as acetoxy groups and butyryloxy groups, carboxy groups, and aromatic ring groups such as phenyl groups and naphthyl groups. The number is preferably 8 or less.

  A represents a structural site that decomposes upon irradiation with actinic rays or radiation to produce an acid. Specifically, photoinitiator for photocationic polymerization, photoinitiator for photoradical polymerization, photodecolorant for dyes, light Examples thereof include a structural portion possessed by a compound that generates acid by known light used in a color changing agent or a microresist.

Examples of the structural site that generates acid upon irradiation with actinic rays or radiation include ionic structural sites possessed by the following photoacid generators.
A diazonium salt described in SI Schlesinger, Photogr. Sci. Eng., 18,387 (1974), TSBal et. Al., Polymer, 21, 423 (1980) and the like.
DCNecker et. Al., Macromolecules, 17, 2468 (1984), CSWen et. Al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent Nos. 4,069,055, 4,069,056, etc. The phosphonium salt described in 1.
JVCrivello et.al., Macromorecules, 10 (6), 1307 (1977), Chem. & Eng.News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Pat.Nos. 339,049, 410,201, Iodonium salts described in JP-A-2-150,848 and JP-A-2-296,514.

  JVCrivello et. Al., Polymer J. 17, 73 (1985), JVCrivello et. Al .. J. Org. Chem., 43, 3055 (1978), WRWatt et. Al., J. Polymer Sci. , Polymer Chem. Ed., 22,1789 (1984), JVCrivello et.al., Polymer Bull., 14,279 (1985), JVCrivello et.al., Macromorecules, 14 (5), 1141 (1981), JV Crivello et.al., J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patents 370,693, 3,902,114, 233,567, 297,443, 297,442, U.S. Patents Sulfonium salts described in 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Korean Patents 2,904,626, 3,604,580, 3,604,581 and the like.

Selenonium salts described in JVCrivello et. Al., Macromorecules, 10 (6), 1307 (1977), JVCrivello et. Al., J. PolymerSci., Polymer Chem. Ed., 17, 1047 (1979).
Onium salts such as arsonium salts described in CSWen et. Al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988).

  A is preferably an ionic structural site, more preferably a structural site containing a sulfonium salt or an iodonium salt.

A is more preferably a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin. In this case, since the acid generated from the repeating unit (A) is supported on the resin, the diffusibility of the acid is suppressed, and the resolution and roughness characteristics can be improved. A is particularly preferably represented by the following general formula (ZI) or (ZII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 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 an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion. Examples of the non-nucleophilic anion 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. As a result, the temporal stability of the resin is improved, and the temporal stability of the resist is also improved.

Examples of the organic group as R ₂₀₁ , R _202, and R ₂₀₃ correspond to the group represented by (ZI-1), (ZI-2), (ZI-3), or (ZI-4) described later. The group can be mentioned.
More preferable examples of the group represented by (ZI) include (ZI-1) group, (ZI-2) group, (ZI-3) group, and (ZI-4) group described below.
The (ZI-1) group is a group having arylsulfonium as a cation, in which at least one of R _{201 to} R ₂₀₃ in the general formula (ZI) is an aryl group.

All of R ₂₀₁ to R ₂₀₃ may be an aryl group or a part of R ₂₀₁ to R ₂₀₃ is an aryl group and the remainder may be an alkyl group or a cycloalkyl group.
For example, groups corresponding to triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, aryldicycloalkylsulfonium can be exemplified.

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

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

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

Next, the (ZI-2) group will be described.
The (ZI-2) group is a group in which R _{201 to} R ₂₀₃ in the general formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

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

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

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

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

The (ZI-3) group and the (ZI-4) group are groups represented by the following general formula (ZI-3) or (ZI-4), respectively. The (ZI-3) group and the (ZI-4) group have high transparency with respect to the exposure wavelength (193 nm) of ArF. Therefore, the (ZI-3) group and the (ZI-4) group are particularly useful when an actinic ray-sensitive or radiation-sensitive resin is used as one component of the composition for ArF exposure.

In General Formula (ZI-3), M represents an alkyl group, a cycloalkyl group, an aryl group, or a benzyl group, and when having a ring structure, the ring structure is an oxygen atom, a sulfur atom, an ester bond, an amide bond, or It may contain a carbon-carbon double bond.
R _1c and R _2c 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, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
R _x and R _y may combine to form a ring.
At least two of M, R _1c and R _2c may be bonded to form a ring, and the ring structure may contain a carbon-carbon double bond.
Z ⁻ represents a non-nucleophilic anion. Z ⁻ has the same meaning as described for the general formula (ZI).

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.
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
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R _{15 's} may be bonded to each other to form a ring.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ⁻ represents a non-nucleophilic anion. Z ⁻ has the same meaning as described for the general formula (ZI).

First, the compound represented by general formula (ZI-3) is demonstrated.
As described above, M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when having a ring structure, the ring structure is an oxygen atom, a sulfur atom, an ester atom, an amide bond or a carbon-carbon double bond. Bonds may be included.

  The alkyl group as M may be linear or branched. The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of such an alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2- Mention may be made of an ethylhexyl group.

  The cycloalkyl group as M preferably has 3 to 12 carbon atoms. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group.

  The aryl group as M preferably has 5 to 15 carbon atoms. Examples of such an aryl group include a phenyl group and a naphthyl group.

  Each group as M may have a cycloalkyl group, an alkoxy group, a halogen atom, a phenylthio group, or the like as a substituent. The cycloalkyl group and aryl group as M may have an alkyl group as a substituent. These substituents preferably have 15 or less carbon atoms.

  When M is a phenyl group, it preferably has at least one alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, or phenylthio group as a substituent. In this case, the sum of the carbon number of the substituents is more preferably 2-15. When such a configuration is adopted, the solubility of the acid generator in the solvent is improved, and the generation of particles during storage can be further suppressed.

Each of R _1c and R _{2c represents} a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group as described above.
This alkyl group may be linear or branched. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 5 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, and a linear or branched propyl group.

  A cycloalkyl group is a C3-C12 cycloalkyl group, for example, Preferably, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group etc. can be mentioned.

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

The aryl group as R _1c and R _2c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

As described above, at least two of M, R _1c and R _2c may be bonded to each other to form a ring. As this ring, Preferably it is 3-12 membered ring, More preferably, it is 3-10 membered ring, More preferably, 3-6 membered ring is mentioned. This ring may have a carbon-carbon double bond.

When R _1c and R _2c are combined to form a ring, the group formed by combining R _1c and R _2c 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 _1c and R _2c may have a heteroatom such as an oxygen atom in the ring.

Each of R _x and R _{y represents} an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, a cycloalkoxycarbonylmethyl group, an allyl group, or a vinyl group, as described above.

Examples of the alkyl group include those described above as the alkyl groups for R _1c and R _2c .
The cycloalkyl group is preferably one having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group.

  Examples of the 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group.

  The alkoxy group part of the alkoxycarbonylmethyl group may be linear or branched. The alkoxy group moiety preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Examples of such an alkoxy group include a methoxy group, an ethoxy group, a linear or branched propoxy group, a linear or branched butoxy group, and a linear or branched pentoxy group.

  The cycloalkoxy group part of the cycloalkoxycarbonylalkyl group preferably has 3 to 8 carbon atoms. Examples of such a cycloalkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. Moreover, as an alkyl group in an alkoxycarbonylalkyl group, a C1-C12 alkyl group is mentioned, for example, Preferably it is a C1-C5 linear alkyl group, for example, a methyl group and an ethyl group are mentioned. be able to.

As described above, R _x and R _y may be bonded to each other to form a ring. Examples of the group formed by combining R _x and R _y with each other include alkylene groups such as a butylene group and a pentylene group.
The allyl group is not particularly limited, but is preferably an allyl group substituted with an unsubstituted monocyclic or polycyclic cycloalkyl group.
The vinyl group is not particularly limited, but is preferably a vinyl group substituted with an unsubstituted monocyclic or polycyclic cycloalkyl group.

Each of R _x and R _y is preferably an alkyl group having 4 or more carbon atoms, more preferably an alkyl group having 6 or more carbon atoms, and still more preferably an alkyl group having 8 or more carbon atoms.

Examples of Z ⁻ in general formula (ZI-3) include the same anions as described above for general formula (ZI-3).
Specific examples of the cation in general formula (ZI-3) are shown below.

Next, the structural moiety represented by the general formula (ZI-4) will be described.
The alkyl group of R ₁₃ , R ₁₄ and R ₁₅ may be linear or branched. This alkyl group preferably has 1 to 10 carbon atoms. Examples of such an alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n- Examples include pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group. Of these, a methyl group, an ethyl group, an n-butyl group, and a t-butyl group are particularly preferable.

Examples of the cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl and cyclooctadienyl groups. It is done. Of these, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl groups are particularly preferred.

The alkoxy group of R ₁₃ and R ₁₄ may be linear or branched. This alkoxy group preferably has 1 to 10 carbon atoms. Examples of such alkoxy groups include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n- Examples include pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group and n-decyloxy group. Of these, a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group are particularly preferable.

The alkoxycarbonyl group of R ₁₃ and R ₁₄ may be linear or branched. The alkoxycarbonyl group preferably has 2 to 11 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, and a 1-methylpropoxycarbonyl group. T-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n- Nonyloxycarbonyl group and n-decyloxycarbonyl group are mentioned. Of these, a methoxycarbonyl group, an ethoxycarbonyl group, and an n-butoxycarbonyl group are particularly preferable.

The group having a monocyclic or polycyclic cycloalkyl skeleton represented by R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, and more preferably a total carbon number of 7 or more and 15 or less.

  Examples of the group having a monocyclic or polycyclic cycloalkyl skeleton include a monocyclic or polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. A group having a cycloalkyl skeleton is preferred. These groups may further have a substituent.

  Examples of the monocyclic cycloalkyloxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloptyloxy group, a cyclooctyloxy group, and a cyclododecanyloxy group. These groups include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a dodecyl group, a 2-ethylhexyl group, an isopropyl group, a sec-butyl group, alkyl groups such as tert-butyl and iso-amyl groups; hydroxyl groups: halogen atoms such as fluorine, chlorine, bromine and iodine atoms; nitro groups; cyano groups; amide groups; sulfonamide groups; Group, propoxy group, alkoxy group such as hydroxypropoxy group and butoxy group; alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; acyl group such as formyl group, acetyl group and benzoyl group; acyloxy group such as acetoxy group and butyryloxy group A group; or a carboxy group It can have.

  Examples of the polycyclic cycloalkyloxy group include a norbornyloxy group and an adamantyloxy group.

  As described above, the monocyclic or polycyclic cycloalkyloxy group preferably has a total carbon number of 7 or more. That is, it is preferable to employ a configuration in which the total of the carbon number of the cycloalkyloxy group mentioned above and the carbon number of the above substituent is 7 or more.

  Examples of the alkoxy group having a monocyclic cycloalkyl group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropoxy, sec-butoxy, t-butoxy And an alkoxy group such as an iso-amyloxy group substituted with a monocyclic cycloalkyl group. This monocyclic cycloalkyl group may further have the above-described substituents. Examples thereof include a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, and the like, and a cyclohexylmethoxy group is preferable.

  Examples of the polycyclic cycloalkyloxy group include a norbornyloxy group and an adamantyloxy group.

  As described above, the alkoxy group having a monocyclic or polycyclic cycloalkyl group preferably has a total carbon number of 7 or more. That is, it is preferable to employ a configuration in which the sum of the number of carbon atoms of the alkoxy group, the number of carbon atoms of the monocyclic cycloalkyl group, and the number of carbon atoms of the above substituents is 7 or more.

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 for R ₁₄ may be linear or branched.
The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ preferably have 1 to 10 carbon atoms. Examples of such alkylsulfonyl group and cycloalkylsulfonyl group include methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, n-butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group, neopentane. Examples include sulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group, n-nonanesulfonyl group, n-decanesulfonyl group, cyclopentanesulfonyl group and cyclohexanesulfonyl group. It is done. Of these, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, and a cyclohexanesulfonyl group are particularly preferable.

  Each of the above groups may further have a substituent. Examples of the substituent include halogen atoms such as fluorine atoms, hydroxy groups, carboxy groups, cyano groups, nitro groups, alkoxy groups, cycloalkoxy groups, alkoxyalkyl groups, cycloalkoxyalkyl groups, alkoxycarbonyl groups, cycloalkoxycarbonyls. Group, alkoxycarbonyloxy group and cycloalkoxycarbonyloxy group. Of these, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, and a halogen atom are more preferable. As the halogen atom, a fluorine atom is particularly preferable.

The alkoxy group may be linear or branched. Examples of the alkoxy group include carbon numbers such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, and t-butoxy group. The thing of 1-20 is mentioned.
Examples of the cycloalkoxy group include those having 4 to 20 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group.

  The alkoxyalkyl group may be linear or branched. Examples of the alkoxyalkyl group include those 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. Is mentioned.

  Examples of the cycloalkoxyalkyl group include a cyclopentyloxymethyl group and a cyclopentyloxymethylethoxy group.

The alkoxycarbonyl group may be linear or branched. 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 and t. -A thing with 2-21 carbon atoms, such as a butoxycarbonyl group, is mentioned.
Examples of the cycloalkoxycarbonyl group include those having 4 to 21 carbon atoms such as a cyclopentyloxycarbonyl group and a cyclohexyloxycarbonyl group.

The alkoxycarbonyloxy group may be linear or branched. Examples of the alkoxycarbonyloxy group include carbon such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group and t-butoxycarbonyloxy group. The thing of 2-21 is mentioned.
Examples of the cycloalkoxycarbonyloxy group include those having 4 to 21 carbon atoms such as a cyclopentyloxycarbonyloxy group and a cyclohexyloxycarbonyloxy group.

Examples of the ring structure that can be formed by combining two R ₁₅ with each other include, for example, a 5-membered ring or a 6-membered ring, particularly preferably a 5-membered ring (that is, tetrahydro) together with the S atom in the general formula (1-1). A structure that forms a thiophene ring).

  This ring structure may further have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group.

As R ₁₅ , a methyl group, an ethyl group, a 1-naphthyl group, and a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom are particularly preferable.

The l is preferably 0 or 1, and more preferably 1.
The r is preferably 0-2.

Below, the preferable specific example of the cation site | part contained in the structure site | part represented by general formula (1-1) is shown.

In the general formula (ZII), R ₂₀₄ ~R ₂₀₅ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Aryl group R ₂₀₄ to R _207, an alkyl group, etc. Specific examples and preferred embodiments of the cycloalkyl group, aryl group R ₂₀₁ to R ₂₀₃ in the compound of the aforementioned (ZI-1), alkyl group, cycloalkyl group This is the same as the aryl group described.

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI-1) may have.

Z ⁻ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion, and examples thereof include the same as Z ⁻ in the general formula (ZI).

As A, the group represented by the following general formula (ZCI) or (ZCII) is also mentioned as a preferred example.

In the above general formula (ZCI),
R ₃₀₁ and R ₃₀₂ each independently represents an organic group.
Carbon number of the organic group as R ₃₀₁ and R ₃₀₂ is generally 1 to 30, preferably 1 to 20.

R _{301 to} R ₃₀₂ 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. Examples of the group formed by bonding include an alkylene group (for example, a butylene group and a pentylene group).
Specific examples of the organic group for R ₃₀₁ and R ₃₀₂ include an aryl group, an alkyl group, a cycloalkyl group, and the like given as examples of R _{201 to} R ₂₀₃ in the general formula (ZI).

  M represents an atomic group which a proton gives to form an acid. More specifically, it is a structure represented by general formulas AN1 to AN4 described later, and among these, the structure represented by AN1 is preferable.

R ₃₀₃ represents an organic group. The organic group as R ₃₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Specific examples of the organic group for R ₃₀₃ include an aryl group, an alkyl group, a cycloalkyl group, and the like given as specific examples of R ₂₀₄ and R ₂₀₅ in the general formula (ZII).

  Moreover, as a structural site | part which generate | occur | produces an acid by irradiation of actinic light or a radiation, the structural site | part used as the sulfonic acid precursor which the following photoacid generator has can be mentioned, for example.

For example,
M.TUNOOKA et.al., Polymer Preprints Japan, 35 (8), G.Berner et.al., J.Rad.Curing, 13 (4), WJMijs et.al., Coating Technol., 55 (697) , 45 (1983), Akzo, H. Adachiet. Al., Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122 U.S. Pat.Nos. 618,564, 4,371,605, and 4,431,774, JP-A-64-18143, JP-A-2-245756, JP-A-4-365048, etc. A compound that generates sulfonic acid by photolysis, such as

Disulfone compounds described in JP-A No. 61-166544.
Furthermore, VNRPillai, Synthesis, (1), 1 (1980), A. Abad et. Al., Tetrahedron Lett., (47) 4555 (1971), DHR Barton et. Al., J. Chem. Soc., (C ), 329 (1970), U.S. Pat. No. 3,779,778, European Patent 126,712 and the like.

Specific examples of the repeating unit (A) are given below.

  When using the composition containing resin (P) for ArF exposure, it is preferable that at least a part of the repeating unit (A) does not contain an aromatic ring other than a naphthalene ring. When using the composition containing resin (P) for EB or EUV exposure, it is preferable that at least a part of the repeating unit (A) contains an aromatic ring from the viewpoint of secondary electron generation efficiency.

As the repeating unit (A), one type may be used alone, or two or more types may be used in combination.
The content of the repeating unit (A) is preferably in the range of 0.5 to 80 mol%, more preferably in the range of 1 to 60 mol%, still more preferably 3 to 40, based on all the repeating units of the resin. It is in the range of mol%.

  When the composition containing the resin (P) is used for ArF exposure, the content of the repeating unit (A) containing an aromatic ring other than the naphthalene ring is 0 to 80 mol% with respect to all the repeating units of the resin. Is preferable, more preferably in the range of 0 to 60 mol%, still more preferably in the range of 0 to 40 mol%.

  When the composition containing the resin (P) is used for EB or EUV exposure, the content of the repeating unit (A) containing an aromatic ring group is 0.5 to 80 mol relative to all the repeating units of the resin. % Is preferable, more preferably in the range of 1 to 60 mol%, still more preferably in the range of 1 to 40 mol%.

[Repeating unit (B)]
The resin (P) contains a repeating unit (B) having a group that decomposes by the action of an acid to generate an alkali-soluble group.
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.

Examples of the group leaving with an acid include -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, each of R _{36 to} R ₃₉ independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, a group obtained by combining an alkylene group and a monovalent aromatic ring group, or alkenyl. Represents a group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R _{01 to} R ₀₂ are each independently a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring 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 Represents.

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 monovalent aliphatic hydrocarbon ring 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), and R ₅₂ in this case 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 represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may combine with each other to form a ring. However, no R ₅₅ and R ₅₆ are hydrogen atoms at the same time.

The general formula (V) will be described in more detail.
The alkyl group represented by R _{51 to} R ₅₃ in the general formula (V) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may 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 R _{51 to} R ₅₃ described above.

The monovalent aliphatic hydrocarbon ring group may be monocyclic or polycyclic. Preferably, a monocyclic monovalent aliphatic hydrocarbon ring group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent, may be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

  Preferred substituents in each of the above groups include, for example, alkyl groups, monovalent aliphatic hydrocarbon ring groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups. Group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group 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 preferred. 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 (—CH ₂ —OH), chloromethyl group (—CH ₂ —Cl), fluorine atom (—F), methylene group (forms a ring with L ₅ ), and ethylene group (forms a ring with L ₅ ) are particularly preferred. .

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

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

The monovalent aliphatic hydrocarbon ring group represented by R ₅₅ and R _56, preferably one having 3 to 20 carbon atoms, cyclopentyl, may be of monocyclic and cyclohexyl group, A polycyclic group such as a norbornyl group, an adamantyl group, a tetracyclodecanyl group, or 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 monovalent aliphatic hydrocarbon ring 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 represented by the general formula (V) are shown below, but the present invention is not limited thereto.

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

In general formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring (preferably a 5-membered or 6-membered ring), and R ₆₂ in this case represents an alkylene group.
Ar ₆ represents a divalent aromatic ring group.
Y, when there are a plurality, each independently represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.

General formula (VI) will be described in more detail.
The alkyl group of R _{61 to} R ₆₃ in the general formula (VI) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, and more preferable examples include alkyl groups having 8 or less carbon atoms.

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

The monovalent aliphatic hydrocarbon ring group may be monocyclic or polycyclic, and preferably has 3 to 8 carbon atoms such as a cyclopropyl group, cyclopentyl group, or cyclohexyl group, which may have a substituent. And a monocyclic monovalent aliphatic hydrocarbon ring group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.

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

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

Examples of the substituent that the alkyl group, the monovalent aliphatic hydrocarbon ring group, the alkoxycarbonyl group, the alkylene group, and the divalent aromatic ring group may have include R _{51 to} R ₅₃ in the general formula (V). Specific examples similar to the substituents which each group represented by can have are given.

n is preferably 1 or 2, and more preferably 1.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of n represents a group capable of leaving by the action of an acid.
Examples of the group Y leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ). ), -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ) -C (= O) -O-C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —CH (R ₃₆ ) (Ar) and the like can be mentioned.

In the formula, each of R _{36 to} R ₃₉ independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, a group obtained by combining an alkylene group and a monovalent aromatic ring group, or an alkenyl group. Represents. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ and R ₀₂ are each independently a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring 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 Represents.

  Ar represents a monovalent aromatic ring group.

The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, octyl group and the like.

The monovalent aliphatic hydrocarbon ring group for R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably an aliphatic hydrocarbon ring group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, an aliphatic hydrocarbon ring group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, A tetracyclododecyl group, an androstanyl group, etc. can be mentioned. In addition, a part of carbon atoms in the aliphatic hydrocarbon ring group may be substituted with a hetero atom such as an oxygen atom.

The monovalent aromatic ring group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ and Ar is preferably a monovalent aromatic ring group having 6 to 10 carbon atoms, for example, aryl such as phenyl group, naphthyl group, anthryl group And a divalent aromatic ring group containing a heterocyclic ring such as a group, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.

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

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

The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. As the monocyclic type, an aliphatic hydrocarbon ring structure having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. Can do. As the polycyclic type, an aliphatic hydrocarbon ring structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. A part of carbon atoms in the aliphatic hydrocarbon ring structure may be substituted with a hetero atom such as an oxygen atom.

The above groups as R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar may have a substituent. Examples of the substituent include an alkyl group and a monovalent aliphatic hydrocarbon ring group. , Aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc. The number of carbon atoms of the substituent is preferably 8 or less.
As the group Y leaving by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

Here, L ₁ and L ₂ are each independently a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, or a group in which an alkylene group and a monovalent aromatic ring group are combined. Represents.

  M represents a single bond or a divalent linking group.

  Q is an alkyl group, a monovalent aliphatic hydrocarbon ring group that may contain a hetero atom, a monovalent aromatic ring group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, or a cyano group. Or represents an aldehyde group.

At least two of Q, M, and L ₁ may combine to form a ring (preferably a 5-membered or 6-membered ring).

The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Preferred examples include a group and an octyl group.

The monovalent aliphatic hydrocarbon ring group as L ₁ and L ₂ is, for example, an aliphatic hydrocarbon ring group having 3 to 15 carbon atoms, specifically, a cyclopentyl group, a cyclohexyl group, a norbornyl group, An adamantyl group etc. can be mentioned as a preferable example.

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

Group formed by combining an alkylene group and a monovalent aromatic ring group represented by L ₁ and L ₂ are, for example, a 6 to 20 carbon atoms, a benzyl group, an aralkyl group such as a phenethyl group.

The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.), a divalent aliphatic hydrocarbon ring group (for example, cyclohexane). Pentylene group, cyclohexylene group, adamantylene group, etc.), alkenylene group (eg, ethylene group, propenylene group, butenylene group, etc.), divalent aromatic ring group (eg, phenylene group, tolylene group, naphthylene group, etc.), A divalent linking group in which —S—, —O—, —CO—, —SO ₂ —, —N (R ₀ ) —, and a combination thereof are combined. R ₀ represents a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group). Octyl group, etc.).

The alkyl group as Q is the same as the above-described groups as L ₁ and L ₂ .
The monovalent aliphatic hydrocarbon ring group which may contain a hetero atom as Q and the aliphatic hydrocarbon ring group which does not contain a hetero atom in a monovalent aromatic ring group which may contain a hetero atom Examples of the monovalent aromatic ring group not containing a hetero atom include the above-described monovalent aliphatic hydrocarbon ring groups as L ₁ and L ₂ , and monovalent aromatic ring groups. It is C3-C15.

  Examples of the monovalent aliphatic hydrocarbon ring group containing a hetero atom and the monovalent aromatic ring group containing a hetero atom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, and imidazole. , Benzimidazole, triazole, thiadiazole, thiazole, pyrrolidone, and other groups having a heterocyclic structure, but generally called a heterocyclic ring (a ring formed of carbon and a heteroatom, or a ring formed of a heteroatom ), It is not limited to these.

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

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

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

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

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

  The actinic ray-sensitive or radiation-sensitive resin (P) may further contain a repeating unit other than the repeating units (A) and (B).

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

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

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic aliphatic hydrocarbon ring 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 aliphatic hydrocarbon ring 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 following general formulas (LC1-1) to (LC1-17). 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).

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

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

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

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

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

As for the content rate of the repeating unit which has an alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in resin (P), More preferably, it is 0-15 mol%, More preferably, it is 0-10 mol%.
Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

In the case of exposure with KrF excimer laser light, electron beam, X-ray, or high energy light (EUV, etc.) having a wavelength of 50 nm or less, an alkali-soluble group having an aromatic ring group is preferable. The structure represented is more preferred.

Here, R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring 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 represented by R ₄₁ , R ₄₂ , and R ₄₃ in formula (IV), a monovalent aliphatic hydrocarbon ring group, a halogen atom, an alkoxycarbonyl group, and a substituent that these groups may have include: Specific examples similar to the respective groups in the above general formula (V) can be given.

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

Preferred substituents in each of the above groups are alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, etc., aryl groups such as phenyl groups, and the like mentioned for R _{51 to} R _53. Groups.

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

The preferred content when the repeating unit (D) is represented by the general formula (IV) is preferably from 3 to 90 mol%, more preferably from 5 to 80 mol%, based on all repeating units in the resin (P). More preferably, it is 7-70 mol%.
Although the specific example of the repeating unit which has an alkali-soluble group represented by general formula (IV) below is shown, this invention is not limited to this. In formula, a represents the integer of 1-2.

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

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

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

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

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

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

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

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

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

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

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

  Examples of the protecting group include an alkyl group, a monovalent aliphatic hydrocarbon ring 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.

R ₅ may be an aryl group or an aralkyl group.
As the aryl group, those having 6 to 12 carbon atoms are preferable, and specific examples include a phenyl group, a naphthyl group, and a biphenyl group. The aryl group may be further substituted with an alkyl group, a cycloalkyl group or the like.

  As the aralkyl group, those having 7 to 15 carbon atoms are preferable, and specific examples include a benzyl group, a naphthylmethyl group, and a naphthylethyl group. The aralkyl group may be further substituted with an alkyl group, a cycloalkyl group or the like.

  The content of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability is preferably 0 to 40 mol%, more preferably based on all repeating units in the resin (P). 0 to 20 mol%.

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

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

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
As a result, the performance required for the resin used in the composition of the present invention, particularly solubility in coating solvent, film-forming property (glass transition point), alkali developability, film slippage (selection of hydrophilicity / hydrophobicity, alkali-soluble group) Fine adjustments such as adhesion of the unexposed part to the substrate and dry etching resistance can be performed.

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

  In the resin (P) used in the composition of the present invention, the 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.

The form of the resin (P) may be any of random type, block type, comb type, and star type.
[Synthesis Method of Resin (P)]
Resin (P) is a basic compound formed from a reaction system containing a monomer (MA) corresponding to repeating unit (A) and a monomer (MB) corresponding to repeating unit (B). It is synthesized by polymerizing in the presence of In addition, this reaction system may contain the monomer corresponding to the various repeating unit mentioned above as a copolymerization component.

  The present inventors have found that the purity of the resulting resin (P) is not necessarily high when the polymerization reaction of these monomers is performed by a conventional method. Therefore, the present inventors conducted various studies to solve this new problem. As a result, the present inventors have found that the purity of the resulting resin (P) is dramatically improved by allowing a basic compound to coexist in the reaction system.

  The reason for this is not always clear, but the present inventors speculate as follows. That is, when the above reaction is performed, the repeating unit (A) or the monomer (MA) is contained in the acid and / or raw material monomer generated by decomposition during the reaction. A trace amount of acid may be present in the system. These acids may decompose some of the acid-decomposable groups of the repeating unit (B) or monomer (MB) during the reaction. Therefore, when the polymerization reaction of these monomers is performed by a conventional method, that is, when the above reaction is performed without the coexistence of a basic compound, the purity of the obtained resin (P) is lowered. On the other hand, when the polymerization reaction is performed in the presence of a basic compound, at least a part of the acid is trapped by the basic compound, and decomposition of the acid-decomposable group can be effectively suppressed. Therefore, this improves the purity of the resin (P) obtained.

  The above reaction may be a radical polymerization reaction or a cation or anion polymerization reaction. In addition, this reaction may be performed by a batch polymerization method in which the monomer and the polymerization initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer and the polymerization initiator is added to the heated solvent. You may carry out by the dripping polymerization method added dropwise over 1 to 10 hours. Of these, the dropping polymerization method is preferred.

(Monomer)
A monomer (MA) is synthesize | combined as follows, for example. That is, for example, it is synthesized by exchanging an acid anion having a polymerizable unsaturated bond corresponding to the repeating unit (A) and a known onium salt halide.

  More specifically, for example, a metal ion salt (for example, sodium ion, potassium ion, etc.) or an ammonium salt (ammonium, triethylammonium salt, etc.) of an acid having a polymerizable unsaturated bond corresponding to the repeating unit (A) , An onium salt having a halogen ion (chloride ion, bromide ion, iodide ion, etc.) in the presence of water or methanol to carry out an anion exchange reaction, dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone and It can be synthesized by separating and washing with an organic solvent such as tetrahydroxyfuran and water.

  In addition, an anion exchange reaction is performed by stirring in the presence of an organic solvent that can be separated from water, such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone, and tetrahydroxyfuran, and water, followed by separation with water. It can also be synthesized by liquid and washing operations.

In addition, the present inventors are concerned with the present invention when the monomer (MA) has a cation moiety represented by at least one of the following general formulas (ZI-3C) and (ZI-4C). It has been found that the improvement in the purity of the resin (P) when the production method is used becomes more remarkable. Although the reason for this is not always clear, the present inventors have found that the monomer (MA) having the cation moiety or the repeating unit (A) corresponding thereto causes relatively thermal decomposition during the reaction. I guess it is easy.

In general formula (ZI-3C), M, R _1c , R _2c , R _x and R _y have the same meanings as those in general formula (ZI-3).
In general formula (ZI-4C), R ₁₃ , R ₁₄ , R ₁₅ , l and r have the same meanings as those in general formula (ZI-4).
The monomer (MB) and other monomers can be synthesized by a known method. Alternatively, commercially available products may be used as these monomers.

(Basic compound)
The basic compound used in the above polymerization reaction is preferably a nitrogen-containing organic basic compound.
Although the compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(3) is used preferably.

(1) Compound represented by the following general formula (BS-1)

In general formula (BS-1),
Each R independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, or an aralkyl group. However, the case where all three R are hydrogen atoms is excluded. Further, the alkyl group as 3R may be linear or branched. Although carbon number of this alkyl group is not specifically limited, Usually, it is 1-20, Preferably it is 1-12.
In addition, the alkyl group as R may have an oxygen atom in the alkyl chain. That is, the alkyl group as R may contain an oxyalkylene chain. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable.

  The monovalent aliphatic hydrocarbon ring group as R may be monocyclic or polycyclic. The number of carbon atoms of the monovalent aliphatic hydrocarbon ring group is not particularly limited, but is usually 3 to 20, and preferably 5 to 15.

Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20, Preferably it is 7-11. Specific examples include a benzyl group.
In the alkyl group, monovalent aliphatic hydrocarbon ring, aryl group or aralkyl group as R, at least a part of hydrogen atoms may be substituted with a substituent. Examples of the substituent include an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, an aralkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group. Can be mentioned.

  R preferably has a phenoxy group at its end. This phenoxy group is, for example, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, an aryloxy group, or the like. It may have a group.

When R has a phenoxy group at its end, the compound represented by the general formula (BS-1) has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. Is preferred. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is preferable.

  In the compound represented by the general formula (BS-1), it is preferable that only one of three Rs is a hydrogen atom, or all Rs are groups other than hydrogen atoms, and all Rs are hydrogen atoms. It is more preferable that it is a group other than.

  Specific examples of the compound represented by the general formula (BS-1) include tri-n-ethylamine, N, N-diisopropylethylamine, tri-n-butylamine, tri-n-pentylamine, and tri-n-octylamine. , Tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, Methyldioctadecylamine, N- (2-cyanoethyl) diethylamine, N- (2-cyanoethyl) diethanolamine, 2- (2-diethylaminoethoxy) ethanol, 2- (dibutylamino) ethanol, 2-diethylaminoethanol N, N-diethylcyclohexylamine, diethylaminoacetonitrile, N, N-diethylglycine methyl, N, N-diethyl-1-naphthylamine, N, N-dimethyl-1-naphthylamine, N, N-dimethyl-2-naphthylamine, 4′-dimethylaminoacetophenone, N-methylacetanilide, N-methylformanilide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-diethylpropionamide, 1- ( 2-cyanoethyl) -2-pipecoline, 1-acetylpyrrolidine, 1-acetyl-4-piperidone, 1-acetyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-methyl- 2-pyrrolidone, 1-ethyl-2-pi Lidon, 1-phenyl-2-pyrrolidone, 4-acetylmorpholine, N-acetoacetylmorpholine, 1-morpholino-1-cyclohexene, N- (2-cyanoethyl) morpholine, 1- (3-cyanopropyl) pyrrolidine, 4- Ethylmorpholine, 4- (4-cyanophenyl) morpholine, 4-phenylmorpholine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dibutylaniline, N, N-dihexylaniline, 2,6- Diisopropylaniline, 2,4,6-tri (t-butyl) aniline, N- (2-cyanoethyl) -N-ethylaniline, N- (2-cyanoethyl) -N- (2-hydroxyethyl) aniline, N- (2-cyanoethyl) -N-methylaniline, N- (2-cyanoethyl) -N-butylaniline, Examples include 1-acetyl-1,2,3,4-tetrahydroquinoline.

  Specific examples of the case where R contains an oxyalkylene chain include tris (methoxyethoxyethyl) amine and compounds exemplified in column 3, line 60 and thereafter of US Pat. No. 6,040,112.

  Specific examples of R having a phenoxy group at its end include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine. And compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of US Patent Application Publication No. 2007 / 0224539A1.

(2) Compound having a nitrogen-containing heterocyclic structure The heterocyclic structure may or may not have aromaticity. Moreover, you may have two or more nitrogen atoms, Furthermore, you may contain hetero atoms other than nitrogen. Specifically, compounds having an imidazole structure (imidazole, 1-methylimidazole, N-acetylimidazole, 2-phenylimidazole, 1-benzylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.) , Compounds having a piperidine structure (1-acetylpiperidine, N- (2-cyanoethyl) piperidine, 1-cyanomethylpiperidine, 1-ethylpiperidine, N-hydroxyethylpiperidine, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) sebacate), compounds having a pyridine structure (pyridine, 2,6-lutidine, 2-acetylpyridine, 3-acetylpyridine, 4-acetylpyridine, 4-dimethylaminopyridine, 4-cyanopyridine, 4-dimethyla Nopirijin etc.), a compound having an antipyrine structure (antipyrine, hydroxy antipyrine like).

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

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

  The basic compound is more preferably a compound represented by the general formula (BS-1) or a compound having a nitrogen-containing heterocyclic structure.

  In addition, compounds that can be used in the synthesis method according to the present invention include compounds synthesized in Examples of JP-A-2002-363146.

  The basic compound may be synthesized, but may be purchased from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., Sigma-Aldrich and the like.

A basic compound can be used individually or in combination of 2 or more types.
The amount of the basic compound used is preferably 0.01 to 200 mol%, more preferably 0.1 to 100 mol%, and more preferably 1 to 50 mol based on the monomer (MA). More preferably, it is mol%, and most preferably 1-25 mol%. If the amount used is excessively large, the basic compound may remain even if the resin is purified. This can affect the resist performance.

(Polymerization initiator)
The above reaction system usually further contains a polymerization initiator. As the polymerization initiator, for example, radical polymerization initiators such as azo initiators and peroxides are 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 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), and the like. Is mentioned. If desired, the initiator may be added in a plurality of times.

(Reaction solvent)
The above reaction is typically performed in the liquid phase. That is, the above reaction system typically further includes a solvent.
The solvent is not particularly limited as long as it can dissolve each component. For example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, cyclic lactone, chain or cyclic ketone, alkylene Examples include carbonate, alkyl carboxylate, alkyl alkoxyacetate, alkyl pyruvate, and alcohol. Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

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

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

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.
Examples of cyclic lactones include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of chain or cyclic ketones include 2-butanone (methyl ethyl ketone), 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexene-2 ON, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3 -Preferred is methylcycloheptanone.

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

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

  As alcohol, methanol, ethanol, n-propanol, i-propanol, and n-butanol are mentioned preferably, for example.

  Solvents that can be preferably used include 2-butanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene carbonate, methanol, ethanol, i-propanol. It is done. Particularly preferred solvents include 2-butanone, cyclohexanone, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methanol, and i-propanol.

  These solvents may be used alone or in combination of two or more.

  As the reaction solvent, an aprotic solvent is preferably used. In particular, it is preferable to use propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone (CyHx), or methyl ethyl ketone (MEK) as the reaction solvent.

  The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Moreover, you may superpose | polymerize in presence of a chain transfer agent (for example, alkyl mercaptan etc.) as needed.

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

Said manufacturing method may further include the process of refine | purifying the product obtained by reaction.
Specifically, after completion of the reaction, the reaction system 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.

  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. These poor solvents may be used alone or in combination of two or more.

  Reprecipitation is preferably performed twice or more, more preferably twice. Further, the poor solvent for reprecipitation that is repeated twice or more is preferably an organic solvent for the first time and an aqueous solvent for the second time, or an aqueous solvent for the first time and an organic solvent for the second time. The aqueous solvent may be water alone or a mixture of water and an organic solvent.

  In consideration of the residual solvent amount of the resin after subsequent drying, the solvent used as the poor solvent is preferably a solvent having a low boiling point. Preferred are water, methanol, ethanol, i-propanol, heptane, hexane, ethyl acetate, butyl acetate, 1-butanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethyl ether, di-i-propyl ether, cyclopentyl Mention may be made of methyl ether. More preferable examples include water, methanol, i-propanol, heptane, hexane, ethyl acetate, butyl acetate, 1-butanone, and di-i-propyl ether. More preferably, water, methanol, heptane, hexane, and ethyl acetate can be mentioned.

  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 polymer solution can be diluted with a desired solvent after polymerization.
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).

  It is preferable that the resin is once deposited and separated and then dissolved again in a solvent, and the resin is brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, the polymer solution diluted with a solvent as necessary is brought into contact with a hardly soluble or insoluble solvent to precipitate the resin (step a), and the resin is separated from the solution (step b). Then, the resin solution A is prepared again by dissolving in a solvent (step c), and then the resin solution A is contacted with a solvent in which the resin is hardly soluble or insoluble to precipitate a resin solid (step d). It may be a method including separating (step e).

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

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

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

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

<Resin that decomposes by the action of an acid and increases the dissolution rate in an aqueous alkali solution>
The composition according to the present invention may further contain, in addition to the resin (P), a resin that decomposes by the action of an acid to increase the dissolution rate in an alkaline aqueous solution (hereinafter also referred to as “acid-decomposable resin”). Good.
The acid-decomposable resin is a resin having a group (acid-decomposable group) that is decomposed by the action of an acid to generate an alkali-soluble group in the main chain or side chain of the resin or in both the main chain and the side chain. . Among these, a resin having an acid-decomposable group in the side chain is more preferable.

  The acid-decomposable resin is decomposed with an acid into an alkali-soluble resin as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. It is possible to obtain an alkali-soluble resin monomer having a group capable of being decomposed or reacting with an acid-decomposable group by copolymerization with various monomers.

  As the acid-decomposable group, for example, in a resin having an alkali-soluble group such as —COOH group and —OH group, a group in which the hydrogen atom of the alkali-soluble group shown on the left is substituted with a group capable of leaving by the action of an acid is preferable.

  Specifically, the acid-decomposable group is the same as the acid-decomposable group described in the resin (P) of the present invention (for example, the acid-decomposable group described as the repeating unit (B) in the resin (P)). A group can be mentioned as a preferred example.

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

The preferred ranges of molecular weight and dispersity of the acid-decomposable resin are the same as those of the resin (P).
Two or more acid-decomposable resins may be used in combination.
In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the compounding amount in the composition of the acid-decomposable resin excluding the resin (P) is preferably 0 to 70% by mass in the total solid content of the composition, More preferably, it is 0-50 mass%, More preferably, it is 0-30 mass%.

<Resin (B2) having no group capable of decomposing by the action of acid>
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a resin (B2) that does not have a group that decomposes by the action of an acid.
“No acid-decomposable group” means that there is no or very little decomposability due to the action of acid in the image forming process in which the composition of the present invention is usually used, and image formation by substantially acid decomposition It has no group (for example, an acid-decomposable group in the resin (P)) that contributes to the above. Examples of such a resin include a resin having an alkali-soluble group and a resin having a group (b) that is decomposed by the action of an alkali and improves the solubility in an alkali developer.

The resin (B2) is preferably a resin having at least one repeating unit derived from a (meth) acrylic acid derivative and / or an alicyclic olefin derivative.
Examples of the alkali-soluble group contained in the resin (B2) include the same as those described for the acid-decomposable group of the resin (P).

  The group (b) contained in the resin (B2) that decomposes by the action of alkali and increases the solubility in an alkali developer is preferably a lactone group or an acid anhydride group, and more preferably a lactone group. (B) Specific examples of the repeating unit having a group that decomposes by the action of an alkali and increases the solubility in an alkali developer include the same repeating units as those having a lactone group in the resin (P). .

  The resin (B2) may have a repeating unit having a functional group other than the above. As the repeating unit having another functional group, an appropriate functional group can be introduced in consideration of dry etching resistance, hydrophilicity / hydrophobicity, interaction property and the like.

Specific examples of preferred resin (B2) are shown below.

The content of the resin (B2) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and still more preferably 0 to 15% by mass with respect to the resin (P).
The preferred range of the molecular weight and the degree of dispersion of the resin (B2) is the same as that of the resin (P).
As the resin (B2), a commercially available one can be used, or one synthesized in the same manner as the resin (P) can be used.

<Compound that generates acid upon irradiation with actinic ray or radiation (low molecular photoacid generator)>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (P) having a photoacid generating structure, but generates an acid by irradiation with actinic rays or radiation in addition to the resin (P). A low molecular weight compound (hereinafter also referred to as “acid generator” or “photoacid generator”).

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

Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.
Preferable examples of the photoacid generator include compounds represented by the following general formulas (ZI), (ZII) and (ZIII).

In the general formula _(ZI), R _{201, R 202} and _{R 203} are the same meaning as _{R 201, R 202} and _{R 203} in the above general formula (ZA-1).
X ⁻ represents a non-nucleophilic anion. Examples of X ⁻ include a sulfonate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ^—, and SbF ₆ ^— . X ⁻ is preferably an organic anion containing a carbon atom. Examples of preferable organic anions include organic anions represented by the following general formulas AN1 to AN3.

In the formula _AN1~AN3, Rc 1 ~Rc ₃ independently represents an organic group. Examples of the organic group include those having 1 to 30 carbon atoms, preferably an alkyl group, an aryl group, or a group in which a plurality of these groups are linked by a single bond or via a linking group. Examples of the linking group include —O—, —CO ₂ —, —S—, —SO ₃ —, and —SO ₂ N (Rd ₁ ) —. Here, Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with a bonded alkyl group or aryl group.

The organic group of Rc _{1 to} Rc ₃ may be an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By containing a fluorine atom or a fluoroalkyl group, it becomes possible to increase the acidity of the acid generated by light irradiation. Thereby, the sensitivity of the actinic ray-sensitive or radiation-sensitive resin composition can be improved. Rc _{1 to} Rc ₃ may be bonded to other alkyl groups and aryl groups to form a ring structure.

As the photoacid generator, a compound having a plurality of structures represented by the general formula (ZI) may be used. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI), at least one coupling structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

Hereinafter, general formulas (ZII) and (ZIII) will be described.
In formula (ZII) and (ZIII), R ₂₀₄ ~R ₂₀₇ each independently represents an aryl group, an alkyl group or a monovalent aliphatic hydrocarbon ring group. These aryl group, alkyl group and monovalent aliphatic hydrocarbon ring group may have a substituent.

The aryl group as R ₂₀₄ to R _207, preferred examples of the alkyl group, and a monovalent aliphatic hydrocarbon ring group, similar to that listed for R ₂₀₄ and R ₂₀₅ in the above general formula (ZA-2) The group of is mentioned.

Incidentally, X in the general formula (ZII) ^- is, X in formula (ZI) ^- is synonymous.

Other preferred examples of the photoacid generator include compounds represented by the following general formula (ZIV), (ZV) or (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents a substituted or unsubstituted aryl group.
R ₂₀₈ represents an alkyl group, a cycloalkyl group, or an aryl group independently in the general formulas (ZV) and (ZVI). These alkyl group, cycloalkyl group and aryl group may be substituted.
These groups are preferably substituted with a fluorine atom. By substituting the fluorine atom, it is possible to increase the strength of the acid generated by the photoacid generator.

R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an electron-withdrawing group. These alkyl group, cycloalkyl group, aryl group and electron-withdrawing group may be substituted.
A represents an alkylene group, an alkenylene group or an arylene group. These alkylene group, alkenylene group and arylene group may have a substituent.

A compound having a plurality of structures represented by the general formula (ZVI) is also preferable as the photoacid generator. Such compounds, for example, binding to _{R 209} or _{R 210} of the compound represented by the general formula (ZVI), and the _{R 209} or _{R 210} of another compound represented by the general formula (ZVI) together And a compound having the above structure.

As the photoacid generator, compounds represented by the general formulas (ZI) to (ZIII) are more preferable, compounds represented by the general formula (ZI) are more preferable, and among them, a cation structure in the general formula (ZI) is preferable. The compounds represented by the general formulas (ZI-1) to (ZI-3) are particularly preferable.
Below, the specific example of a photo-acid generator is shown.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, when an acid generator is used in addition to the resin (P) having a photoacid generating structure, the acid generator is used alone or in combination of two. The above can be used in combination. The content of the acid generator in the composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and still more preferably 0 to 7% by mass, based on the total solid content of the composition of the present invention. is there. The acid generator is not an essential component in the present invention, but is usually used in an amount of 0.01% by mass or more in order to obtain the effect of addition.

<Hydrophobic resin (HR)>
The composition according to the present invention may further contain a hydrophobic resin. When the hydrophobic resin is further contained, the hydrophobic resin is unevenly distributed on the surface layer of the film formed using this composition, and the receding contact angle of the film with respect to the immersion liquid is improved when water is used as the immersion liquid. It becomes possible. Thereby, the immersion liquid followability of a film | membrane can be improved.

  The hydrophobic resin typically contains fluorine atoms and / or silicon atoms. These fluorine atoms and / or silicon atoms may be contained in the main chain of the resin or may be contained in the side chain.

  When the hydrophobic resin contains a fluorine atom, the resin has a partial structure containing a fluorine atom as an alkyl group containing a fluorine atom, a monovalent aliphatic hydrocarbon ring group containing a fluorine atom, or fluorine. It is preferable to have an aryl group containing an atom.

  The alkyl group containing a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.

  The monovalent aliphatic hydrocarbon ring group containing a fluorine atom is a monocyclic or polycyclic monovalent aliphatic hydrocarbon ring group in which at least one hydrogen atom is substituted with a fluorine atom. The cycloalkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.

  An aryl group containing a fluorine atom is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom. Examples of the aryl group include a phenyl group and a naphthyl group. The aryl group containing a fluorine atom may further have a substituent other than the fluorine atom.

Preferred examples of the alkyl group containing a fluorine atom, the monovalent aliphatic hydrocarbon ring group containing a fluorine atom, and the aryl group containing a fluorine atom include groups represented by the following general formulas (F2) to (F4) Is mentioned.

In general formulas (F2) to (F4), R _{57 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{57 to} R ₆₁ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{62 to} R ₆₄ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{65 to} R ₆₈ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. These alkyl groups preferably have 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 an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be bonded to each other to form a ring.

  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.

  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, Examples include 3,3-tetrafluorocyclobutyl group and perfluorocyclohexyl group. Among these, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro (2-methyl) isopropyl group, an octafluoroisobutyl group, a nonafluoro-t-butyl group or a perfluoroisopentyl group is more preferable, and a hexafluoroisopropyl group or More preferred is a heptafluoroisopropyl group.

Examples of the group represented by the general formula (F4) include —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, and —CH. (CF ₃ ) OH. Of these, -C (CF _{3) 2} OH is particularly preferred.

Specific examples of the repeating unit containing a fluorine atom are shown below.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents —F or —CF ₃ .

  When the hydrophobic resin contains a silicon atom, the resin preferably has an alkylsilyl structure or a cyclic siloxane structure as a partial structure containing a silicon atom. This allylsilyl structure is preferably a structure containing a trialkylsilyl group.

Preferable examples of the alkylsilyl structure and 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 represents a linear or branched alkyl group or a monovalent aliphatic hydrocarbon ring group. This alkyl group preferably has 1 to 20 carbon atoms. The monovalent aliphatic hydrocarbon ring group preferably has 3 to 20 carbon atoms.

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, a urea group, or a combination thereof.
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

Below, the specific example of the repeating unit provided with group represented by general formula (CS-1)-(CS-3) is given. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

The hydrophobic resin may further include at least one group selected from the group consisting of the following (x) to (z).
(X) Alkali-soluble group (y) Group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer (z) Acid-decomposable group (x) Examples of the alkali-soluble group include phenolic hydroxyl groups , Carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene Groups, bis (alkylcarbonyl) imide groups, bis (alkylsulfonyl) methylene groups, bis (alkylsulfonyl) imide groups, tris (alkylcarbonyl) methylene groups, and tris (alkylsulfonyl) methylene groups. Preferred alkali-soluble groups include fluorinated alcohol groups, sulfonimide groups, and bis (carbonyl) methylene groups. Preferred fluorinated alcohol groups include hexafluoroisopropanol groups.

  The repeating unit having an alkali-soluble group is a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit by acrylic acid and methacrylic acid. Alternatively, this repeating unit may be a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent provided with the alkali-soluble group at the time of superposition | polymerization.

The content of the repeating unit having an alkali-soluble group is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, based on all repeating units in the hydrophobic resin. More preferably, it is -20 mol%.
Specific examples of the repeating unit having an alkali-soluble group are shown below.

  (Y) Examples of the group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer include a group having a lactone structure, an acid anhydride group, and an acid imide group. Of these, a group having a lactone structure is particularly preferable.

  The repeating unit containing this group is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent provided with this group at the time of superposition | polymerization.

  Examples of the repeating unit having a group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer include the same units as the above-mentioned repeating unit (C).

  The content of the repeating unit having a group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is 1 to 40 mol% based on all repeating units in the hydrophobic resin. Is more preferable, it is more preferable that it is 3-30 mol%, and it is still more preferable that it is 5-15 mol%.

Examples of the (z) acid-decomposable group include the same groups as described in the above-mentioned repeating unit (B).
The content of the repeating unit having an acid-decomposable group is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the hydrophobic resin. More preferably, it is -60 mol%.
The hydrophobic resin may further contain a repeating unit represented by the following general formula (III).

In formula (III), R _c31 represents a hydrogen atom, an alkyl group, an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, a cyano group, or a —CH ₂ —O—Rac ₂ group. Here, 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, and particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group containing 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 and / or a silicon atom.

The alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group preferably has 3 to 20 carbon atoms.
The alkenyl group preferably has 3 to 20 carbon atoms.
The cycloalkenyl group preferably has 3 to 20 carbon atoms, and examples thereof include a cycloalkenyl group.

The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
L _c3 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group (preferably having a carbon number of 1 to 5), an oxy group, a phenylene group, and an ester bond (a group represented by —COO—).
The hydrophobic resin may further contain a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-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 necessary for forming an alicyclic structure together with two carbon atoms (C—C) to which R _c11 ′ and R _c12 ′ are bonded.
Specific examples of the repeating unit represented by the general formula (III) or (CII-AB) are given below. In specific examples, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

Specific examples of the hydrophobic resin are given below. Table 1 below summarizes the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

  When the hydrophobic resin contains a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass, more preferably 10 to 80% by mass based on the molecular weight of the hydrophobic resin. . In addition, the content of the repeating unit containing a fluorine atom is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, based on all repeating units of the hydrophobic resin.

  When the hydrophobic resin contains silicon atoms, the silicon atom content is preferably 2 to 50% by mass, more preferably 2 to 30% by mass, based on the molecular weight of the hydrophobic resin. . In addition, the content of the repeating unit containing a silicon atom is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, based on all repeating units of the hydrophobic resin.

One type of hydrophobic resin may be used alone, or two or more types may be used in combination.
In the present invention, a hydrophobic resin is not an essential component, but when a film made of the composition of the present invention is exposed with an ArF excimer laser through an immersion medium, the content of the hydrophobic resin is determined in the composition. Is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and still more preferably 0.1 to 5% by mass.

<Basic compound>
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a basic compound. As this basic compound, for example, the same compounds as those described as the basic compound used in the synthesis of the resin (P) can be used.

<Surfactant>
The composition of the present invention may further contain a surfactant. When contained, the surfactant is preferably a fluorine-based and / or silicon-based surfactant.
Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] et seq. Of US Patent Application Publication No. 2008 / 0248425A1.
Surfactants may be used alone or in combination of two or more.

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

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

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

  As alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone, chain or cyclic ketone, alkylene carbonate, alkyl carboxylate, alkyl alkoxyacetate, and alkyl pyruvate For example, the same thing as having demonstrated the reaction solvent previously is mentioned.

  Preferred solvents that can be used include 2-heptanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid Examples include ethyl, ethyl pyruvate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and propylene carbonate. Particularly preferred solvents include propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether.

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

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

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

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

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

In the general formulas (1) to (6),
R represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group.
R ₀ represents a group capable of leaving by the action of an acid.
R ₁ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group.
R ₂ represents an alkyl group or an aralkyl group.
R ₃ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group.
R ₄ and R ₅ each independently represents an alkyl group, and R ₄ and R ₅ may be bonded to each other to form a ring.

R ₆ represents a hydrogen atom or an alkyl group.
R ₇ represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group.
R ₈ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group.

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

  In the general formulas (1) to (6), examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, and examples of the monovalent aliphatic hydrocarbon ring group include 4 to 10 carbon atoms. Examples thereof include monocyclic or polycyclic aliphatic hydrocarbon ring groups, examples of the aryl group include aryl groups having 6 to 14 carbon atoms, and examples of the aralkyl group include aralkyl groups having 7 to 20 carbon atoms. The alkoxy group includes an alkoxy group having 1 to 8 carbon atoms, the alkenyl group includes an alkenyl group having 2 to 6 carbon atoms, and the aryloxy group includes an aryloxy group having 6 to 14 carbon atoms. Group, and examples of the alkenyloxy group include alkenyloxy groups having 2 to 8 carbon atoms.

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

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

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

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

_R0 : t-butyl group, methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, tetrahydropyranyl group.
R ₁ ; methyl group, ethyl group, propyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, propoxy group, phenoxy group, naphthoxy group.
R ₂ : methyl group, ethyl group, propyl group, butyl group, benzyl group.

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

R ₄ , R ₅ : Methyl group, ethyl group, propyl group, those bonded to each other to form an ethylene group or a propylene group.
R ₆ : hydrogen atom, methyl group, ethyl group.

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

R ₈ ; methyl group, ethyl group, isopropyl group, t-butyl group, neopentyl group, cyclohexyl group, phenyl group, benzyl group.
R ₁₀ : methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, methoxy group, ethoxy group, phenyl group, naphthyl group, benzyl group, phenoxy group, naphthoxy Group formed by forming a 3-oxocyclohexenyl ring or a 3-oxoindenyl ring, which may be bonded to each other to contain an oxygen atom.

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

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

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

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

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

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

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

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

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

[Pattern formation method]
The composition of the present invention is typically used by dissolving the above-described components in a solvent, filtering the solution, and applying the solution to a support.
The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less.
The thickness of the resist film is not particularly limited, but is preferably 0.01 to 0.2 μm, and more preferably 0.02 to 0.1 μm.
As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

  The composition is applied by a suitable application method such as a spinner onto a substrate (eg, silicon / silicon dioxide coating) used for manufacturing an integrated circuit element, a photomask, an imprint mold, and the like. Thereafter, it is dried to form a photosensitive film.

  The film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common.

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

  Although it does not specifically limit as actinic light or a radiation, For example, they are a KrF excimer laser, ArF excimer laser, EUV light, an electron beam etc., ArF excimer laser, EUV light, and an electron beam are preferable.

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

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

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

  The film comprising the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is filled with a liquid (immersion medium) having a higher refractive index than air between the film and the lens when irradiated with actinic rays or radiation. Exposure (immersion exposure) may be performed. Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.

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 a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the resist film. 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-mentioned viewpoints.

  Further, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. 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 resist film on the wafer is not dissolved and the influence on the optical coating on the lower surface of the lens element can be ignored. An 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 specifically includes methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained. On the other hand, when an opaque material or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light, the optical image projected on the resist film is distorted. . Further, pure water filtered through an ion exchange filter or the like may be used.

The electrical resistance of water is desirably 18.3 MQcm or more, the TOC (organic substance concentration) is desirably 20 ppb or less, and deaeration treatment is desirably performed.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

  When exposing the film | membrane which consists of a composition of this invention through an immersion medium, hydrophobic resin (HR) can be further added as needed. As a result, the hydrophobic resin (HR) is unevenly distributed on the surface layer of the film, and when the immersion medium is water, the receding contact angle of the resist film surface with respect to the water when used as a film is improved, and the immersion water followability is improved. Can do. By adding the hydrophobic resin (HR), the receding contact angle of the surface is improved. The receding contact angle of the film before exposure is preferably 60 ° to 90 °, more preferably 70 ° or more. Hydrophobic resin (HR) is unevenly distributed at the interface as described above, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances should be mixed uniformly. It does not have to contribute to

  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 respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

  An immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) may be provided between the film of the composition of the present invention and the immersion liquid so that the film does not directly contact the immersion liquid. Good. The functions necessary for the top coat are suitability for application to the upper layer of the resist, transparency to radiation, particularly 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the upper layer of the resist.

  From the viewpoint of 193 nm transparency, the top coat is preferably a polymer that does not contain abundant aromatics. Specifically, the polymer contains a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, and silicon. Examples include polymers and fluorine-containing polymers. The aforementioned hydrophobic resin (HR) is also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, 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 film is preferable. In terms of being able to perform the peeling process simultaneously with the film development process, it is preferable that the peeling process can be performed with an alkaline developer. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the film.

  The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. In the case of using water as the immersion liquid in an ArF excimer laser (wavelength: 193 nm), the top coat for ArF immersion exposure is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.

  The topcoat is preferably not mixed with the membrane 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 topcoat may be water-soluble or water-insoluble.

  Hereinafter, the embodiments of the present invention will be described in more detail by way of examples.

<Synthesis of Compound (5)>
Compound (5) was synthesized according to the following scheme.

  First, 100.00 g of compound (1) was dissolved in 400 g of ethyl acetate. The resulting solution was cooled to 0 ° C., and 47.60 g of sodium methoxide (28% methanol solution) was added dropwise over 30 minutes. This was then stirred at room temperature for 5 hours. Ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with distilled water and then dried over anhydrous sodium sulfate, and the solvent was distilled off. In this way, 131.70 g of Compound (2) (54% ethyl acetate solution) was obtained.

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

  35.00 g of compound (3) was dissolved in 315 g of methanol, cooled to 0 ° C., 245 g of 1N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 2 hours. After the solvent was distilled off, ethyl acetate was added, and the organic layer was washed 3 times with saturated brine and then dried over anhydrous sodium sulfate, and the solvent was distilled off. In this way, 34.46 g of compound (4) was obtained.

  28.25 g of compound (4) was dissolved in 254.25 g of methanol, 23.34 g of triphenylsulfonium bromide was added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off, distilled water was added, and the mixture was extracted 3 times with chloroform. The obtained organic layer was washed 3 times with distilled water, and then the solvent was distilled off. In this way, 42.07 g of compound (5) was obtained.

  Other monomers (MA) were also synthesized by the same method as described above for compound (5).

  Subsequently, the resins (P-1) to (P-20) listed above were synthesized.

<Synthesis of Resin (P-3)>
Resin (P-3) was synthesized according to the following scheme.

  First, 12.46 g of compound (2) (53.1% propylene glycol monomethyl ether solution), 6.74 g of compound (6), 5.41 g of compound (5), 0.16 g of triethylamine, 1.61 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 29.18 g of propylene glycol monomethyl ether (PGME). 8.80 g of PGME was put in the reaction vessel and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 31 g of acetone. The diluted solution was dropped into 1000 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and filtered. The filtered solid was washed with 250 g of hexane / ethyl acetate = 8/2. The obtained solid was dissolved in 65 g of acetone and dropped into 800 g of methanol / distilled water = 1/9 to precipitate the polymer, followed by filtration. The filtered solid was washed with 200 g of methanol / distilled water = 1/9. Thereafter, the washed solid was subjected to vacuum drying to obtain 14.08 g of resin (P-3).

<Synthesis of Resin (P-3 ′)>
Resin (P-3 ′) was synthesized according to the following scheme.

  12.46 g of compound (2) (53.1% propylene glycol monomethyl ether acetate solution), 6.74 g of compound (6), 5.41 g of compound (5), 0.16 g of triethylamine, 1 .61 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 29.18 g of propylene glycol monomethyl ether acetate (PGMEA). 8.80 g of PGMEA was put in the reaction vessel and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 31 g of acetone. The diluted solution was dropped into 1000 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and filtered. The filtered solid was washed with 250 g of hexane / ethyl acetate = 8/2. The obtained solid was dissolved in 65 g of acetone and dropped into 800 g of methanol / distilled water = 1/9 to precipitate the polymer, followed by filtration. The filtered solid was washed with 200 g of methanol / distilled water = 1/9. Thereafter, the washed solid was dried under reduced pressure to obtain 15.49 g of resin (P-3 ′).

<Synthesis of Resin (P-5)>
Resin (P-5) was synthesized according to the following scheme.

  First, 17.89 g of compound (2) (40.3% propylene glycol monomethyl ether solution), 6.56 g of compound (6), 1.79 g of compound (7), 0.41 g of triethylamine (1 % Propylene glycol monomethyl ether solution) and 2.30 g polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 18.36 g propylene glycol monomethyl ether (PGME). 7.30 g of PGME was put in the reaction vessel, and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 26 g of acetone. The diluted solution was dropped into 780 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and filtered. The filtered solid was washed with 200 g of hexane / ethyl acetate = 8/2. The obtained solid was dissolved in 45 g of acetone and dropped into 560 g of methanol / distilled water = 1/9 to precipitate the polymer, followed by filtration. The filtered solid was washed with 150 g of methanol / distilled water = 1/9. Thereafter, the washed solid was subjected to vacuum drying to obtain 7.86 g of resin (P-5).

<Synthesis of Resin (P-5 ′)>
Resin (P-5 ′) was synthesized according to the following scheme.

  First, 17.89 g of compound (2) (40.3% propylene glycol monomethyl ether solution), 6.56 g of compound (6), 1.79 g of compound (7), 0.41 g of triethylamine (1 % Propylene glycol monomethyl ether solution) and 2.30 g polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 18.36 g propylene glycol monomethyl ether (PGME). 7.30 g of PGME was put in the reaction vessel, and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 26 g of acetone. The diluted solution was dropped into 780 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and filtered. The filtered solid was washed with 200 g of hexane / ethyl acetate = 8/2. Thereafter, the washed solid was dried under reduced pressure to obtain 9.43 g of resin (P-5 ′).

<Synthesis of Resin (P-5 '')>
Resin (P-5 ″) was synthesized according to the following scheme.

  First, 17.89 g of compound (2) (40.3% propylene glycol monomethyl ether solution), 6.56 g of compound (6), 1.79 g of compound (7), 0.41 g of triethylamine (1 % Propylene glycol monomethyl ether solution) and 2.30 g polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 18.36 g propylene glycol monomethyl ether (PGME). 7.30 g of PGME was put in the reaction vessel, and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 26 g of acetone. The diluted solution was dropped into 780 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and filtered. The filtered solid was washed with 200 g of hexane / ethyl acetate = 8/2. The obtained solid was dissolved in 45 g of acetone and added dropwise to 560 g of hexane / ethyl acetate = 8/2 to precipitate the polymer, followed by filtration. The filtered solid was washed with 150 g of hexane / ethyl acetate = 8/2. Thereafter, the washed solid was dried under reduced pressure to obtain 8.55 g of resin (P-5 ″).

<Synthesis of Resin (P-8)>
Resin (P-8) was synthesized according to the following scheme.

  First, 6.56 g of compound (8), 1.18 g of compound (9), 2.73 g of compound (6), 1.31 g of compound (10) and 2.77 g of compound (11) 0.11 g of N- (2-cyanoethyl) -N-methylaniline and 0.37 g of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.), 22.1 g of methyl ethyl ketone (MEK) ). 11.9 g of MEK was placed in the reaction vessel and dropped into the system at 65 ° C. over 6 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 10 g MEK. The diluted solution was dropped into 600 g of methanol to precipitate the polymer and filtered. The filtered solid was washed with 150 g of methanol. Thereafter, the washed solid was dried under reduced pressure to obtain 8.54 g of a resin (P-8).

<Synthesis of Resin (P-9)>
Resin (P-9) was synthesized according to the following scheme.

  First, 1.60 g of compound (8), 0.35 g of compound (9), 1.09 g of compound (6), 2.05 g of compound (12), and 0.07 g of N- (2 -Cyanoethyl) -N-methylaniline and 0.11 g of polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 7.7 g of methyl ethyl ketone (MEK). 4.2 g of MEK was placed in the reaction vessel and dropped into the system at 65 ° C. in a nitrogen gas atmosphere over 4 hours. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

The reaction solution was diluted by adding 4 g MEK. The diluted solution was dropped into 200 g of methanol to precipitate the polymer and filtered. The filtered solid was washed with 50 g of methanol. Thereafter, the washed solid was subjected to vacuum drying to obtain 2.14 g of a resin (P-9).

  First, 3.62 g of compound (8), 0.76 g of compound (9), 1.75 g of compound (6), 0.84 g of compound (10) and 3.29 g of compound (13). Then, 0.30 g of N, N-dimethylformamide and 0.24 g of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 15.5 g of cyclohexanone. 8.4 g of cyclohexanone was placed in the reaction vessel and dropped into the system at 65 ° C. in a nitrogen gas atmosphere over 6 hours. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 7 g of acetone. The diluted solution was dropped into 500 g of methanol to precipitate the polymer and filtered. The filtered solid was washed with 125 g of methanol. The obtained solid was dissolved in 12 g of acetone and dropped into 150 g of methanol to precipitate the polymer, followed by filtration. The filtered solid was washed with 40 g of methanol. Thereafter, the washed solid was dried under reduced pressure to obtain 1.53 g of resin (P-10).

<Synthesis of Resin (P′-1): Comparative Example>
Resin (P′-1) was synthesized according to the following scheme.

  First, 12.46 g of compound (2) (53.1% propylene glycol monomethyl ether solution), 6.74 g of compound (6), 5.41 g of compound (5), and 1.61 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 29.18 g of propylene glycol monomethyl ether (PGME). 8.80 g of PGME was put in the reaction vessel and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 31 g of acetone. The diluted solution was dropped into 1000 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and filtered. The filtered solid was washed with 250 g of hexane / ethyl acetate = 8/2. The obtained solid was dissolved in 65 g of acetone and dropped into 800 g of methanol / distilled water = 1/9 to precipitate the polymer, followed by filtration. The filtered solid was washed with 200 g of methanol / distilled water = 1/9. Thereafter, the washed solid was subjected to vacuum drying to obtain 9.86 g of resin (P′-1).

<Synthesis of Resin (P′-2): Comparative Example>
Resin (P′-2) was synthesized according to the following scheme.

  First, 6.56 g of compound (8), 1.18 g of compound (9), 2.73 g of compound (6), 1.31 g of compound (10) and 2.77 g of compound (11) And 0.37 g of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 22.1 g of methyl ethyl ketone (MEK). 11.9 g of MEK was placed in the reaction vessel and dropped into the system at 65 ° C. over 6 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 10 g MEK. The diluted solution was dropped into 600 g of methanol to precipitate the polymer and filtered. The filtered solid was washed with 150 g of methanol. Thereafter, the washed solid was subjected to reduced pressure drying to obtain 5.98 g of resin (P′-2).

Other resins were synthesized in the presence of a basic compound in the same manner as described for the resin (P-3) and the like. The basic compound and reaction solvent used and the form of reprecipitation are as shown in Table 2 below, and the weight average molecular weight, composition ratio and molecular weight of the obtained resin are as shown in Table 3 below. In the column of “basic compound” in Table 2, the type of the basic compound used for the synthesis of the resin is described. In the column of “Amount of basic compound used (mol%)” in the table, the molar ratio relative to the monomer (MA) is described. In Table 2, in the case where two solvents are used in combination, the numerical value in parentheses is the mixing ratio (mass ratio) of the solvent.

<Resist evaluation>
(Resist preparation)
The following components were mixed, and a solution with a solid content concentration of 4% by mass was prepared for each, and this was filtered through a polyethylene filter having a pore size of 0.05 μm to prepare an actinic ray-sensitive or radiation-sensitive resin composition. .

10g of each resin
Basic compound 0.15 g: 2,6-diisopropylaniline Surfactant 0.01 g: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
Solvent: PGMEA / PGME = 6/4 (mass ratio).

  An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied, and baked at 100 ° C. for 60 seconds to form a film having a thickness of 120 nm. Then, without exposing, it developed for 30 second with the tetramethylammonium hydroxide (TMAH) aqueous solution (2.38 mass%), rinsed with the pure water, Then, it spin-dried.

The film thickness after development was measured, and the remaining film ratio was determined from the following equation. And it evaluated according to the following criteria, and the result was put together in the following Table 4.
Residual film ratio (%) = (film thickness after development / film thickness before development) × 100
(Criteria)
5: When the remaining film ratio is 97.5% or more 4: When the remaining film ratio is 95% or more and less than 97.5% 3: When the remaining film ratio is 92.5% or more and less than 95% 2: Remaining film ratio When 90% or more and less than 92.5% 1: When the remaining film rate is less than 90%

  As can be seen from the results shown in Table 4, in the actinic ray-sensitive or radiation-sensitive resin composition containing the resin (P) obtained by the method according to the present invention, the remaining film ratio with respect to the alkaline developer is greatly improved. did. From this result, it was suggested that the resin (P) obtained by the method according to the present invention hardly decomposes the repeating unit (A) before exposure. That is, it was found that the resin (P) obtained by the method according to the present invention has high purity.

Claims (14)

  1st monomer provided with the structure part which decomposes | disassembles by irradiation of actinic light or a radiation, and generate | occur | produces an acid, and 2nd monomer provided with the group which decomposes | disassembles by the effect | action of an acid and produces an alkali-soluble group A process for producing an actinic ray-sensitive or radiation-sensitive resin comprising polymerizing a reaction system in the presence of a basic compound. 2. The basic compound according to claim 1, wherein the basic compound is at least one selected from the group consisting of a compound represented by the following general formula (BS-1), a compound having a nitrogen-containing heterocyclic structure, and an ammonium salt. Manufacturing method of resin.

In general formula (BS-1),
Each R independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group (except when all three Rs are hydrogen atoms). At least two of the three Rs may be connected to each other to form a ring.   The method for producing a resin according to claim 2, wherein the basic compound is at least one of a compound represented by the general formula (BS-1) and a compound having a nitrogen-containing heterocyclic structure.   The method for producing a resin according to any one of claims 1 to 3, wherein an amount of the basic compound used is 0.01 to 200 mol% with respect to the first monomer.   5. The method for producing a resin according to claim 1, wherein the repeating unit corresponding to the first monomer generates an acid anion in a side chain of the resin upon irradiation with the actinic ray or radiation. The resin according to any one of claims 1 to 5, wherein the first monomer has a cation moiety represented by at least one of the following general formulas (ZI-3C) and (ZI-4C). Production method.

In general formula (ZI-3C),
M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group. When M has a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.
R _1c and R _2c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
At least two of M, R _1c and R _2c may be bonded to each other to form a ring.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. R _x and R _y may be bonded to each other to form a ring.
In general formula (ZI-4C),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.
R ₁₄ 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 group when r ≧ 2. Represents a group having a cycloalkyl skeleton.
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.
l represents an integer of 0-2.
r represents an integer of 0 to 8.   The method for producing a resin according to claim 1, wherein the reaction system further contains an aprotic solvent.   The method for producing a resin according to any one of claims 1 to 7, further comprising purifying the product obtained by the reaction by reprecipitation.   The method for producing a resin according to claim 8, wherein the reprecipitation is repeated twice or more.   The organic solvent is used for the first time and the aqueous solvent is used for the second time, or the aqueous solvent is used for the first time and the organic solvent is used for the second time as a poor solvent in the reprecipitation twice or more. 9. A method for producing a resin according to 9.   The actinic-ray sensitive or radiation sensitive resin obtained by the manufacturing method of any one of Claims 1 thru | or 10.   An actinic ray-sensitive or radiation-sensitive composition comprising the resin according to claim 11.   A resist film formed using the composition according to claim 12. Forming a film using the composition of claim 12;
Exposing the film;
Developing a pattern of the exposed film.