JP5525777B2 - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method using the same, and more particularly to a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrics. The present invention relates to an actinic ray-sensitive or radiation-sensitive composition used in an application process and a pattern forming method using the same. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitable for using far-ultraviolet rays and electron beams of 250 nm or less, preferably 220 nm or less as an exposure light source, and pattern formation using the same. It is about the method.

  In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.

As an actinic ray-sensitive or radiation-sensitive resin composition, a so-called chemical amplification type positive photosensitive composition generates an acid in an exposed area by irradiation with radiation such as far ultraviolet light, and a reaction using this acid as a catalyst. And a pattern forming material for changing the solubility of the active radiation irradiated portion and the non-irradiated portion in the developer to form a pattern on the substrate.
Along with the high integration and high speed of LSI, there is a demand for miniaturization of pattern rules, and far-ultraviolet lithography is promising as a fine processing technique, and its application has already started. Far-ultraviolet lithography can process 0.2 μm or less, and when a resist material with low light absorption is used, it is possible to form a pattern having sidewalls that are nearly perpendicular to the substrate. In recent years, a technique using high-brightness KrF and ArF excimer lasers as a deep ultraviolet light source has attracted attention. In order to be used as a mass-production technique, a resist material with low light absorption and high sensitivity is required. ing.
In addition, as in Patent Documents 1 and 2, a basic compound is generally added to a chemically amplified resist in order to suppress a change in performance over time after exposure.
Patent Document 3 discloses a resist material in which a compound having an amine oxide structure is added to a chemically amplified resist in order to improve resolution, pattern collapse, and etching resistance.
Even in the chemically amplified resist as described above, it has been desired to suppress development defects in forming a fine pattern, to suppress line edge roughness, and to provide a wide exposure latitude.

JP 2002-214774 A JP 2008-170983 A JP 2008-102383 A

As a result of various studies by the present inventors, a basic compound added to a chemically amplified resist to suppress performance change with time after exposure is generated by deprotection of the polymer by exposure and subsequent heating. It has been found that it forms a salt with carboxylic acid and contributes to development defects. The present inventors have found an additive that enables good resist performance without depending on the addition of a conventional basic compound, and have completed the present invention.
An object of the present invention is to solve the problems of the technology for improving the performance of microphotofabrication using far-ultraviolet light, EUV, electron beam, etc., especially ArF excimer laser light, and normal exposure and liquid immersion. In patterning by exposure, development defects can be suppressed, line edge roughness can be suppressed, exposure latitude is wide, and an excellent actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method using the same It is to provide.

一般式（Ｉ）中、
Ｒ _１ は、水素原子、置換基を有していてもよいメチル基又は−ＣＨ _２ −Ｒ _９ で表される基を表す。Ｒ _９ は１価の有機基を表す。
Ｒ _２ は、アルキル基又はシクロアルキル基を表す。
Ｒは、炭素原子とともに脂環構造を形成するのに必要な原子団を表す。
一般式（Ａ）中、Ｒ _０１ 、Ｒ _０２ 及びＲ _０３ は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。Ａｒ _１ は、芳香環基を表す。なお、Ｒ _０３ とＡｒ _１ とがアルキレン基であり、両者が互いに結合することにより、−Ｃ−Ｃ−鎖と共に、５員又は６員環を形成していてもよい。
ｎ個のＹは、各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Ｙの少なくとも１つは、酸の作用により脱離する基を表す。
ｎは、1〜４の整数を表す。
〔２〕
上記（Ｂ）酸の作用によりアルカリ現像液に対する溶解速度が増大する樹脂が、上記一般式（Ａ）で表される繰り返し単位を有し、上記一般式（Ａ）において、Ｙが、下記一般式（Ｂ）で表される基であることを特徴とする〔１〕に記載の組成物。

式中、Ｌ _１ 及びＬ _２ は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基又はアラルキル基を表す。
Ｍは、単結合又は２価の連結基を表す。
Ｑは、アルキル基、脂環基、芳香環基、アミノ基、アンモニウム基、メルカプト基、シアノ基又はアルデヒド基を表す。なお、これら脂環基及び芳香環基は、ヘテロ原子を含んでいてもよい。
なお、Ｑ、Ｍ、Ｌ _１ の少なくとも２つが互いに結合して、５員又は６員環を形成していてもよい。
〔３〕
上記一般式（Ｂ）において、−（Ｍ−Ｑ）で表される基が、炭素数５〜２０の基であることを特徴とする〔２〕に記載の組成物。
〔４〕
上記（Ｂ）酸の作用によりアルカリ現像液に対する溶解速度が増大する樹脂が、ラクトン基を有する繰り返し単位を有することを特徴とする〔１〕〜〔３〕のいずれかに記載の組成物。
〔５〕
（Ａ）活性光線又は放射線の照射に酸を発生する化合物、（Ｂ）酸の作用によりアルカリ現像液に対する溶解速度が増大する樹脂、及び（Ｃ）ラジカルトラップ基を有する化合物を含有する感活性光線性又は感放射線性樹脂組成物であって、上記（Ｂ）酸の作用によりアルカリ現像液に対する溶解速度が増大する樹脂が、ラクトン基を有する繰り返し単位を有し、上記（Ｃ）ラジカルトラップ基を有する化合物が、窒素酸素結合を有する化合物であることを特徴とする感活性光線性又は感放射線性樹脂組成物。
〔６〕
更に疎水性樹脂を含有することを特徴とする〔１〕〜〔５〕のいずれかに記載の組成物。
〔７〕
上記（Ｃ）ラジカルトラップ基を有する化合物が、下記一般式（１）〜（３）のいずれかで示す化合物であることを特徴とする〔１〕〜〔６〕のいずれかに記載の組成物。

一般式中、Ｒ _１ 〜Ｒ ₆ は、それぞれ独立に、アルキル基、シクロアルキル基、又はアリール基を表す。式（１）においてＲ _１ 及びＲ ₂ が結合して環を形成していても良く、式（３）においてＲ ₄ 〜Ｒ ₆ の少なくとも二つが結合して環を形成していても良い。
〔８〕
上記（Ｃ）ラジカルトラップ基を有する化合物が、上記一般式（２）で示す化合物であることを特徴とする〔７〕に記載の組成物。
〔９〕
〔１〕〜〔８〕のいずれかに記載の組成物により形成される膜。
〔１０〕
〔９〕に記載の膜を露光、現像する工程を含むことを特徴とするパターン形成方法。
本発明は、上記〔１〕〜〔１０〕に関するものであるが、以下、その他の事項についても記載した。
The present inventors have found that the above problem can be achieved by using a compound having a radical trap group instead of the nitrogen-containing basic compound used in a normal actinic ray-sensitive or radiation-sensitive resin composition. The present invention shown has been completed. Although the effect of the present invention is not clear, the radical trap group suppresses acid generation at an earlier stage than a normal acid-base reaction, and forms a salt with an acid group on the resin because it is a non-basic compound. It is estimated that there is an improvement effect on image performance and development defects.
[1]
(A) a compound capable of generating an acid upon irradiation with actinic rays or radiation, (B) a resin capable of increasing the dissolution rate in an alkali developer by the action of an acid, and (C) an actinic ray containing a compound having a radical trap group A resin having a repeating unit represented by the following general formula (I) or (A), wherein the resin (B) has a dissolution rate increased in an alkaline developer by the action of the acid. And (C) the compound having a radical trap group is a compound having a nitrogen-oxygen bond, an actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (I),
R ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a monovalent organic group.
R ₂ represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
In general formula (A), R ₀₁ , R ₀₂ and R ₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Ar ₁ represents an aromatic ring group. Note that R ₀₃ and Ar ₁ are alkylene groups, and they may be bonded to each other to form a 5-membered or 6-membered ring together with the —C—C— chain.
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 Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.
[2]
The resin (B) whose dissolution rate in an alkaline developer increases by the action of the acid has a repeating unit represented by the general formula (A). In the general formula (A), Y represents the following general formula The composition according to [1], which is a group represented by (B).

In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, an alicyclic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. In addition, these alicyclic groups and aromatic ring groups may contain a hetero atom.
In addition, at least two of Q, M, and L ₁ may be bonded to each other to form a 5-membered or 6-membered ring.
[3]
In the above general formula (B), the group represented by-(MQ) is a group having 5 to 20 carbon atoms.
[4]
(B) The resin according to any one of [1] to [3], wherein the resin whose rate of dissolution in an alkaline developer is increased by the action of an acid has a repeating unit having a lactone group.
[5]
(A) a compound capable of generating an acid upon irradiation with actinic rays or radiation, (B) a resin capable of increasing the dissolution rate in an alkali developer by the action of an acid, and (C) an actinic ray containing a compound having a radical trap group Or a radiation-sensitive resin composition, wherein the resin (B) whose dissolution rate in an alkaline developer is increased by the action of an acid has a repeating unit having a lactone group, and the (C) radical trap group An actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound having a nitrogen-oxygen bond is included.
[6]
The composition according to any one of [1] to [5], further comprising a hydrophobic resin.
[7]
The composition according to any one of [1] to [6], wherein the compound (C) having a radical trap group is a compound represented by any one of the following general formulas (1) to (3): .

In the general formula, R _{1 to} R ₆ each independently represents an alkyl group, a cycloalkyl group, or an aryl group. In Formula (1), R ₁ and R ₂ may be bonded to form a ring, and in Formula (3), at least two of R _{4 to} R ₆ may be bonded to form a ring.
[8]
The composition according to [7], wherein the compound (C) having a radical trap group is a compound represented by the general formula (2).
[9]
The film | membrane formed with the composition in any one of [1]-[8].
[10]
The pattern formation method characterized by including the process of exposing and developing the film | membrane as described in [9].
The present invention relates to the above [1] to [10], but other matters are also described below.

<1> (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a resin that increases the dissolution rate in an alkali developer by the action of the acid, and (C) a compound having a radical trap group. An actinic ray-sensitive or radiation-sensitive resin composition.
<2> The composition according to <1>, wherein the compound (C) having a radical trap group is a compound having a nitrogen-oxygen bond.
<3> The composition according to <1> or <2>, further comprising a hydrophobic resin.
<4> The compound having a radical trap group (C) is a compound represented by any one of the following general formulas (1) to (3), wherein any of the above <1> to <3> The composition as described.

In the general formula, R _{1 to} R ₆ each independently represents an alkyl group, a cycloalkyl group, or an aryl group. In Formula (1), R ₁ and R ₂ may be bonded to form a ring, and in Formula (3), at least two of R _{4 to} R ₆ may be bonded to form a ring.
<5> A pattern forming method comprising: forming a film using the composition according to any one of <1> to <4>, and exposing and developing the film.

  According to the present invention, development defects can be suppressed and line edge roughness can be suppressed, and an excellent fine pattern can be formed with a wide exposure latitude. The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is particularly suitable as a positive resist composition.

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

[1] (A) Photoacid generator The present invention contains a compound (photoacid generator) that decomposes upon irradiation with actinic rays or radiation to generate an acid. Photoacid generator includes photoinitiator for photocationic polymerization, photoinitiator for photoradical polymerization, photodecoloring agent for dyes, photochromic agent, irradiation of actinic ray or radiation used for micro resist, etc. The known compounds that generate an acid and mixtures 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.

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

Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712, etc. can also be used.
Preferred examples of the acid generator include compounds represented by the following general formulas (ZI), (ZII), and (ZIII). Among these, at least one compound represented by the general formula (ZI) is preferable. It is preferable to use more than one species.

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 a non-nucleophilic anion.

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

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. Thereby, the temporal stability of the actinic ray-sensitive or radiation-sensitive resin composition is improved.

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

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

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

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

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

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

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

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

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

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

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

Further, the acid generator is preferably a compound that generates an acid having one sulfonic acid group or imide group, more preferably a compound that generates monovalent perfluoroalkanesulfonic acid, or a monovalent fluorine atom or fluorine atom. A compound that generates an aromatic sulfonic acid substituted with a group that contains a monovalent fluorine atom or a compound that generates an imide acid substituted with a group containing a fluorine atom, or a monovalent fluorine atom or fluorine atom It is a compound that generates a methide acid substituted with a contained group, and still more preferably a fluoride-substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted imide acid, or a sulfonium salt of a fluorine-substituted methide acid. The acid generator is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid, or a fluorinated substituted imido acid having a pKa of the generated acid of pKa = -1 or less, and the sensitivity is improved.
Examples of the counter ion represented by X ⁻ include a structure represented by the following general formula (II).

In general formula (II), A represents an oxygen atom, a nitrogen atom, or a carbon atom.
R ₁ represents a monovalent organic group containing a fluorine atom.
R ₂ represents a fluorine atom, an alkyl group, a cycloalkyl group, or an aryl group.
When A is an oxygen atom, n = 1, m = 0, when A is a nitrogen atom, n + m = 2 and n = 1 or 2, m = 0 or 1, and when A is a carbon atom, n + m = 3 and n = 1-3, m = 0-2. When n is 2 or more, R ₁ may be the same or different, and R ₁ may be bonded to each other to form a ring.

General formula (II) will be described in more detail.
Examples of the monovalent organic group containing a fluorine atom represented by R ₁ include an organic group containing an alkylene part substituted with at least one fluorine atom bonded to a sulfonyl group, and the alkylene part is a perfluoroalkylene. More preferably, it is a group. Moreover, it is preferable that the group which has a cyclic structure is substituted for the terminal, and you may substitute through the coupling group. From the viewpoint of low fluorine content, the group having this cyclic structure preferably does not contain a fluorine atom. In one embodiment, the monovalent organic group represented by R ₁ includes a structure corresponding to R ₁ represented by the following general formula (III).

The alkyl group, cycloalkyl group, and aryl group represented by R ₂ represent a chain alkyl group, a monocyclic alkyl group, a polycyclic hydrocarbon group, or a monocyclic aryl group, and the chain alkyl group The monocyclic alkyl group, the polycyclic hydrocarbon group, and the monocyclic aryl group may have a substituent. The substituent preferably has a fluorine atom.
The chain alkyl group may be linear or branched, and is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, 2-ethylhexyl, isopropyl, sec-butyl, t-butyl, iso -Amyl etc. are mentioned.

Examples of monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloptyl, cyclooctyl, cyclododecanyl, cyclobenthenyl, cyclohexenyl, cyclooctadienyl, and the like, particularly cyclopropyl, cyclopentyl, cyclohexyl, Cyclooctyl is preferred.
Examples of polycyclic hydrocarbon groups include bicyclo [4.3.0] nonanyl, decahydronaphthalenyl, tricyclo [5.2.1.0 (2,6)] decanyl, bornyl, isobornyl, norbornyl, adamantyl, noradamantyl, 1,7 , 7-trimethyltricyclo [2.2.1.0 ^2,6 ] heptanyl, 3,7,7-trimethylbicyclo [4.1.0] heptanyl and the like, and norbornyl, adamantyl and noradamantyl are particularly preferable.

A monocyclic aryl group means a substituted or unsubstituted phenyl group.
Examples of the substituent that the chain alkyl group, monocyclic alkyl group, polycyclic hydrocarbon group or monocyclic aryl group as R ₂ may have include a hydroxyl group, a halogen atom (fluorine, chlorine, Bromine, iodine), nitro group, cyano group, amide group, sulfonamide group, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and other alkyls Group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group and other alkoxy groups, methoxycarbonyl group, ethoxycarbonyl group and other alkoxycarbonyl groups, formyl group, acetyl group, benzoyl group and other acyl groups Group, an acetoxy group, an acyloxy group such as a butyryloxy group, and a carboxy group. However, a hydroxyl group is excluded as a substituent that the chain alkyl group as R ₂ may have.

R ₂ preferably has an electron-withdrawing group from the viewpoint of acid strength. The electron-withdrawing group is not particularly limited, but is a cyano group, a trifluoromethyl group, a nitro group, a carboxyl group, a ketone group, Examples include acyloxy groups, hydroxy groups, perfluoroalkyl groups, methoxy groups, ethoxy groups, isopropoxy groups, t-butoxy groups, alkoxy groups such as benzyloxy groups, halogen atoms such as fluorine atoms and chlorine atoms, etc. It preferably has a fluorine atom. More preferred is a group having a fluorine atom having a molecular weight of 220 or less, and particularly preferred is a trifluoromethyl group.

  The counter anion represented by the general formula (II) is preferably a structure represented by the following general formula (III).

In the general formula _{(III), A, R 2} , m, n are as defined above in the general formula (II).
When there are a plurality of R _{3 s} , each independently represents an alkyl group, a cycloalkyl group or an aryl group, and R ₄ represents a hydrogen atom.
L represents a single bond or a linking group.
p1 represents an integer of 1 to 8, p2 = 1 or 2, and p3 = 0 or 1.
When p2 = 2, two R ₃ may be bonded to each other to form a ring structure, and when n = 2 or more, a plurality of R ₃ may be bonded to each other to form a ring structure.
Specific examples of the alkyl group, cycloalkyl group and aryl group represented by R ₃ include the same groups as those exemplified for each of R ₂ .
Here, R ₃ preferably has no fluorine atom.

L is a single bond, an oxygen atom (—O—), a sulfur atom (—S—), a nitrogen atom (> N—), a carboxyl group (—OC═O—, —CO═O—), an amide group (> NC = O—) and a sulfonamide group (> NSO ₂ —) are preferable. In particular, a p2 = 2, when two R ₃ join to form a ring together, preferably L is a linking group having an amide group, the nitrogen atom such as a sulfonamide group, two where R ₃ combine with each other to form a cyclic amine residue having a nitrogen atom on L in the ring. Cyclic amine residue structures include aziridine, azetidine, pyrrolidine, piperidine, hexamethyleneimine, heptamethyleneimine, piperazine, decahydroquinoline, decahydroquinoline, 8-azabicyclo [3.2.1] octane, indole, oxazolidine, thiazolidine, 2 -Azanorbornane, 7-azanorbornane, morpholine, thiamorpholine and the like may be mentioned, and these may have a substituent. Substituents include hydroxyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), nitro groups, cyano groups, amide groups, sulfonamido groups, methyl groups, ethyl groups, propyl groups, n-butyl groups, sec-butyl groups. , Hexyl group, 2-ethylhexyl group, alkyl group such as octyl group, alkoxy group such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, alkoxy group such as methoxycarbonyl group, ethoxycarbonyl group, etc. Examples include carbonyl groups, formyl groups, acetyl groups, benzoyl groups, acyl groups such as carbonyl groups on the carbon forming the ring, acyloxy groups such as acetoxy groups and butyryloxy groups, and carboxy groups.
Examples of the counter anion structure represented by the general formula (II) of the present invention include the following specific examples.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI) include corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later. be able to.

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

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

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

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or R ₂₀₁
Some of to R ₂₀₃ is an aryl group and the remainder may be an alkyl group or a cycloalkyl group.

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

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

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

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

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

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

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

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

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

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

  The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

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

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

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

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

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

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

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

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c , such as a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxy group. A carbonylmethyl group is more preferred.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .
Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as in R _{1c to} R _5c .

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

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

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group.

When a plurality of R ₁₄ are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, or a cycloalkylsulfonyl group.

R ₁₅ each independently represents an alkyl group or a cycloalkyl 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 10.

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

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

Examples of the cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclobenenyl, cyclohexenyl, cyclooctadienyl and the like. In particular, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl are preferred.

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

The alkoxycarbonyl group for R ₁₃ is linear or branched and preferably has 2 to 11 carbon atoms, and examples thereof include alkoxycarbonyl groups corresponding to the alkoxy groups exemplified as R ₁₃ and R _14. Can do. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

The alkylsulfonyl group and cycloalkylsulfonyl group for R ₁₄ are linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms. For example, alkyls exemplified as R ₁₃ , R _14, and R ₁₅ Mention may be made of alkylsulfonyl groups and cycloalkylsulfonyl groups corresponding to groups or cycloalkyl groups. Of these alkylsulfonyl groups and cycloalkylsulfonyl groups, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, a cyclohexanesulfonyl group, and the like are preferable.

  l is preferably 0 or 1, and more preferably 1. As r, 0-2 are preferable.

Examples of the substituent that each group of R ₁₃ , R ₁₄ , and R ₁₅ may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, and an alkoxy group. An alkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group and the like can be mentioned, and preferably has 21 or less carbon atoms.

As the ring structure that two R ₁₅ may be bonded to each other, a 5- or 6-membered ring, particularly preferably a 5-membered ring (that is, a 5-membered ring together with the sulfur atom in the general formula (ZI-4) (that is, A group that forms a tetrahydrothiophene ring) is desirable. Examples of the substituent for the divalent group include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.
Below, the preferable specific example of the cation in the compound represented by general formula (ZI-4) is shown.

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

The alkyl group and cycloalkyl group in R ₂₀₄ to R _207, 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).

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

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).
Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group. R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.

  Among acid generators, particularly preferred examples are given below.

The (A) photoacid generator may be used alone or in combination.
The (A) photoacid generator is preferably contained in an amount of 1 to 60% by mass, more preferably 3 to 50% by mass, and more preferably 3 to 35% by mass with respect to the total solid content in the composition of the present invention. It is particularly preferred that it be included.

[2] (B) Resin whose dissolution rate in an alkaline developer is increased by the action of an acid The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin whose solubility in an alkaline developer is increased by the action of an acid. (B) is contained.

Resins whose acid solubility is increased by the action of an acid (acid-decomposable resins) are decomposed into the main chain or side chain of the resin or both the main chain and the side chain by the action of an acid, resulting in an alkali-soluble group. (Hereinafter also referred to as “acid-decomposable group”).
The resin (B) is preferably insoluble or hardly soluble in an alkali developer.

The acid-decomposable group preferably has a structure protected with a group capable of decomposing and leaving an alkali-soluble group by the action of an acid.
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 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, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

  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.

  The repeating unit having an acid-decomposable group that can be contained in the resin (B) is preferably a repeating unit represented by the following general formula (AI).

In general formula (AI),
Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxy group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. . Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group or a — (CH ₂ ) ₃ — group.
The alkyl group of Rx _{1 to} Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.

Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group A polycyclic cycloalkyl group such as a group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are combined to form the above-described cycloalkyl group is preferred.

  Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, An alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.

  The content of the repeating unit having an acid-decomposable group as a total is preferably 20 to 70 mol%, more preferably 30 to 50 mol%, based on all repeating units in the resin.

  Although the specific example of the repeating unit which has a preferable acid-decomposable group is shown below, this invention is not limited to this.

In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality thereof, each is independent, for example, a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, or at least one of these, A linear or branched alkyl group or a cycloalkyl group may be mentioned. p represents 0 or a positive integer.

  The resin (B) is a resin having at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably.

In formulas (I) and (II),
R ₁ and R ₃ each independently represents a hydrogen atom, an optionally substituted methyl group or a group represented by —CH ₂ —R ₉ . R ₉ represents a monovalent organic group.
R ₂ , R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.

R ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The alkyl group in R ₂ may be linear or branched, and may have a substituent. The cycloalkyl group in R ₂ may be monocyclic or polycyclic, may have a substituent, and part of the methylene group may be replaced with an oxygen atom or a sulfur atom. R ₂ is preferably an alkyl group or a polycyclic cycloalkyl group, more preferably 1 to 10 carbon atoms,
More preferably, it is a C1-C7 thing, for example, a methyl group, an ethyl group, and an oxanorbornyl group are mentioned.
R ₂ is preferably an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.

  R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, and more preferably 5 or 6.

R ₃ is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

The alkyl group in R ₄ , R ₅ and R ₆ may be linear or branched and may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

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

In formula (II-1),
R < ₃ > -R < ₅ > is synonymous with the thing in general formula (II).

R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent containing a polar group include a hydroxyl group, a cyano group, an amino group, an alkylamide group, a sulfonamide group, or a linear or branched alkyl group or cycloalkyl group having at least one of them. An alkyl group having a hydroxyl group is preferable. As the branched alkyl group, an isopropyl group is particularly preferable.

  p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

When the resin (B) uses an acid-decomposable repeating unit in combination, the combination of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II), represented by a different general formula (I) A combination of two or more repeating units is preferable, and more preferable combinations are listed below. In the following formula, each R independently represents a hydrogen atom or a methyl group.

The resin (B) preferably contains a repeating unit having a lactone structure represented by the following general formula (III).

In formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination thereof when there are a plurality of R ₀ .
When there are a plurality of Zs, each independently represents an ether bond, an ester bond, an amide bond, or a urethane bond.

Or urea bond

Represents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

R ₈ represents a monovalent organic group having a lactone structure.
n is the repeating number of the structure represented by —R ₀ —Z—, and represents an integer of 1 to 5.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

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

The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group in R ₇ may be substituted. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t -Acetoxy groups such as alkoxy groups such as butoxy group and benzyloxy group, acetyl groups and propionyl groups. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

Preferable chain alkylene group in R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. Preferable cycloalkylene is cycloalkylene having 1 to 20 carbon atoms, and examples thereof include cyclohexylene, cyclopentylene, norbornylene, adamantylene and the like. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.

The substituent having a lactone structure represented by R ₈ is not limited as long as it has a lactone structure, and is represented by general formulas (LC1-1) to (LC1-17) described later as specific examples. Among them, the structure represented by (LC1-4) is particularly preferable. Further, n ₂ in (LC1-1) to (LC1-17) is more preferably 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or a monovalent organic group having a lactone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) as is more preferable.

Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (III) are shown below, but the present invention is not limited thereto.
In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

  The repeating unit having a lactone structure is more preferably a repeating unit represented by the following general formula (III-1).

In general formula (III-1),
R ₇ , A, R ₀ , Z, and n are as defined in the general formula (III).
R ₉ independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, when there are a plurality of R _{9 s} , May be formed.

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

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

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

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

Specific examples of the repeating unit having a group having a lactone structure represented by formula (III-1) are shown below, but the present invention is not limited thereto. In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

  The content of the repeating unit represented by the general formula (III) is preferably 15 to 60 mol%, more preferably 20 to 60 mol%, and more preferably 20 to 60 mol% with respect to all repeating units in the resin when a plurality of types are contained. Preferably it is 30-50 mol%.

The resin (B) may contain a repeating unit having a lactone group in addition to the unit represented by the general formula (III).

  Any lactone group can be used as long as it has a lactone structure, but it is preferably a 5- to 7-membered ring lactone structure, and forms a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure. The other ring structure is preferably condensed. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and (LC1-17). By using this lactone structure, LER and development defects are improved.

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 cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

As the repeating unit having a lactone structure other than the unit represented by the general formula (III), a repeating unit represented by the following general formula (AII ′) is also preferable.

In general formula (AII ′),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. 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. Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferred.

V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).
Specific examples of the repeating unit having a lactone group other than the unit represented by the general formula (III) are shown below, but the present invention is not limited thereto.

Examples of the repeating unit having a lactone group other than the unit represented by the general formula (III) include the following repeating units. By selecting an optimal lactone group, the pattern profile and the density dependency are improved.

  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 having a lactone other than the repeating unit represented by the general formula (III) is preferably 15 to 60 mol% in total with respect to all the repeating units in the resin when more than one type is contained, more preferably Is 20 to 50 mol%, more preferably 30 to 50 mol%.

In order to enhance the effect of the present invention, two or more lactone repeating units selected from general formula (III) can be used in combination. When using together, it is preferable to select and use 2 or more types from the lactone repeating unit whose n is 1 among general formula (III).

The resin (B) preferably has a repeating unit having a hydroxyl group or a cyano group other than the general formulas (AI) and (III). This improves the substrate adhesion and developer compatibility. 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 preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

In 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 remaining is a hydrogen atom. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the remaining are hydrogen atoms.

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

In the general formulas (AIIa) to (AIId), 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.

The content of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (B).

  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 used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron withdrawing group at the α-position. It is more preferable to have a repeating unit. 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 (B), More preferably, it is 3-15 mol%, More preferably, it is 5-10 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 .

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

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic 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 cyclic 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 preferred 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. It is done. 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 the substituent which may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino protected with a protecting group The group can be mentioned.

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

The content of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability is preferably 0 to 40 mol%, more preferably based on all repeating units in the resin (B). 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 (B) used in the composition 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 necessary characteristics of the resist. Various repeating structural units can be included for the purpose of adjusting the resolution, heat resistance, sensitivity, and the like.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, performance required for the resin used in the composition of the present invention, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

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

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin (B) used in the composition of the present invention, the content molar ratio of each repeating structural unit is dry etching resistance, standard developer suitability, substrate adhesion, profile, and general required performances such as resolution and heat resistance. It is appropriately set to adjust the property, sensitivity, etc.

When the composition of the present invention is for ArF exposure, the resin (B) used in the composition of the present invention preferably has no aromatic group from the viewpoint of transparency to ArF light. ) Preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In addition, it is preferable that resin (B) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin (HR) mentioned later.

The resin (B) used in the composition of the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.
Moreover, the alicyclic hydrocarbon substituted by the (meth) acrylate type repeating unit 20-50 mol% which has an acid-decomposable group, the (meth) acrylate type repeating unit 20-50 mol% which has a lactone group, and a hydroxyl group or a cyano group. A copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a structure and further containing 0 to 20 mol% of another (meth) acrylate-based repeating unit is also preferred.

  In the case where the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray or high energy light having a wavelength of 50 nm or less (for example, EUV), this resin preferably has a hydroxystyrene repeating unit. . More preferably, the resin is a copolymer of hydroxystyrene and hydroxystyrene protected with a group capable of leaving by the action of an acid, or a copolymer of hydroxystyrene and a (meth) acrylic acid tertiary alkyl ester. It is.

  Specific examples of such a resin include a resin (B ′) having a repeating unit represented by the following general formula (A).

In the formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Ar ₁ represents an aromatic ring group, for example. Note that R ₀₃ and Ar ₁ are alkylene groups, and they may be bonded to each other to form a 5-membered or 6-membered ring together with the —C—C— chain.

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 Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4, preferably 1 to 2, and more preferably 1.

The alkyl group as R _{01 to} R ₀₃ is, for example, an alkyl group having 20 or less carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a hexyl group. , 2-ethylhexyl group, octyl group or dodecyl group. More preferably, these alkyl groups are alkyl groups having 8 or less carbon atoms. In addition, these alkyl groups may have a substituent.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R _{01 to} R ₀₃ described above.

The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Preferably, a C3-C8 monocyclic cycloalkyl group, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is mentioned. In addition, these cycloalkyl groups 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.

When R ₀₃ represents an alkylene 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.

The aromatic ring group as Ar ₁ preferably has 6 to 14 carbon atoms, and examples thereof include a benzene ring, a toluene ring and a naphthalene ring. In addition, these aromatic ring groups may have a substituent.

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 ) and And a group represented by —CH (R ₃₆ ) (Ar).

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R36 and R37 may be bonded to each other to form a ring structure.

R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
Ar represents an aryl group.

The alkyl group as R _{36 to} R ₃₉ , R ₀₁ , or R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- A butyl group, a hexyl group, and an octyl group are mentioned.

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

The aryl group as R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ , or Ar is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

The aralkyl group as R _{36 to} R ₃₉ , R ₀₁ , or R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and for example, a benzyl group, a phenethyl group, and a naphthylmethyl group are preferable.

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

The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkane structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. As the polycyclic type, a cycloalkane 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. Note that some of the carbon atoms in the ring structure may be substituted with a heteroatom such as an oxygen atom.

  Each of the above groups may have a substituent. Examples of this substituent include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, and acyloxy groups. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.

  As the group Y leaving by the action of an acid, a structure represented by the following general formula (B) is more preferable.

In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, an alicyclic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. In addition, these alicyclic groups and aromatic ring groups may contain a hetero atom.
In addition, at least two of Q, M, and L ₁ may be bonded to each other to form 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, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and An octyl group is mentioned.
The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
The aryl group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specifically includes a phenyl group, a tolyl group, a naphthyl group, and an anthryl group.
The aralkyl group as L ₁ and L ₂ is, for example, an aralkyl group having 6 to 20 carbon atoms, and specific examples include a benzyl group and 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 or octylene group), cycloalkylene group (for example, cyclopentylene group or cyclohexylene group). ), an alkenylene group (e.g., an ethylene group, a propenylene group or a butenylene group), an arylene group (e.g., phenylene, tolylene or naphthylene group), - S -, - O -, - CO -, - SO 2 -, - N (R ₀ ) — or a combination of two or more thereof. Here, R ₀ is a hydrogen atom or an alkyl group. The alkyl group as R ₀ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. Can be mentioned.

The alkyl group as Q is the same as the alkyl group as L ₁ and L ₂ described above.

Examples of the alicyclic group or aromatic ring group as Q include the cycloalkyl group and aryl group as L ₁ and L ₂ described above, and preferably a group having 3 to 15 carbon atoms.

  Examples of the alicyclic group or aromatic ring group containing a hetero atom as Q include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole. And a group having a heterocyclic structure such as pyrrolidone. However, the ring is not limited to these as long as it is a ring formed of carbon and a heteroatom, or a ring formed only of a heteroatom.

Examples of the ring structure that can be formed by bonding at least two of Q, M, and L ₁ to each other include a 5-membered or 6-membered ring structure in which these form a propylene group or a butylene group. This 5-membered or 6-membered ring structure contains an oxygen atom.

Each group represented by L ₁ , L ₂ , M and Q in the general formula (B) may have a substituent. Examples of this substituent include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, and acyloxy groups. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.
The group represented by-(MQ) is preferably a group having 1 to 30 carbon atoms, and more preferably a group having 5 to 20 carbon atoms. In particular, from the viewpoint of outgas suppression, a group having 6 or more carbon atoms is preferable.

  Preferable resin (B ′) further includes a resin having a repeating unit represented by the general formula (AI).

  The content of the repeating unit represented by the general formula (AI) in the resin (B ′) is preferably in the range of 3 to 90 mol%, more preferably 5 to 80 mol based on all repeating units. %, Particularly preferably in the range of 7 to 70 mol%.

Resins suitable for KrF, EB, EUV and the like may have a repeating unit other than the repeating units described above. Preferred examples of this include, for example, a repeating unit that is stable against the action of an acid and a repeating unit having a lactone structure as described below.

Here, as the repeating unit stable to the action of acid, more specifically, the repeating unit represented by the general formula (IV) shown above (wherein R ₅ is a hydrocarbon group, among which In the case of having a cyclic structure, a monocyclic or polycyclic cycloalkyl group (preferably having 3 to 12 carbon atoms, more preferably 3 to 7 carbon atoms), monocyclic or A polycyclic cycloalkenyl group (preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms), and an aralkyl group (preferably having 7 to 20 carbon atoms, more preferably Includes a repeating unit having a non-acid-decomposable aryl structure or a cycloalkyl structure in the side chain of the acrylic structure as shown in FIG. By having this structure, adjustment of contrast, improvement in etching resistance, and the like can be expected.

The content of the repeating unit that is stable with respect to the action of the acid is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, based on all repeating units in the resin (B ′).
Specific examples of the repeating unit that is stable against the action of an acid include the following in addition to the specific examples of the repeating unit represented by the general formula (IV). In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  Examples of the repeating unit having a lactone structure that may be contained in the resin (B ′) include those similar to the repeating unit having a lactone structure that may be contained in the resin (B).

  Although the specific example of resin demonstrated above is shown below, this invention is not limited to these.

In the above specific example, tBu represents a t-butyl group.
The content of the group capable of decomposing with an acid is determined by the formula B according to the number of groups (B) capable of decomposing with an acid in the resin and the number of alkali-soluble groups not protected by a group capable of leaving with an acid (S). / (B + S). This content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

  The resin (B) containing the resin (B ′) may be a commercially available product when commercially available, but can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the actinic-ray sensitive or radiation sensitive resin composition like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is carried out using the same solvent as that used in the actinic ray-sensitive or radiation-sensitive resin composition. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. The concentration of the reaction is 5 to 50% by mass, preferably 30 to 50% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

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

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

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

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

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

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

  The weight average molecular weight of the resin (B) of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3, as a polystyrene conversion value by GPC method. 000 to 15,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

  The dispersity (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 2.0. The smaller the molecular weight distribution, the better the resolution and pattern shape, the smoother the sidewall of the resist pattern, and the better the roughness.

In the present invention, the blending ratio of the resin (B) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content.
In addition, the resins of the present invention may be used alone or in combination.

[3] (RT) Compound having radical trap group The composition of the present invention contains a compound (RT) having a radical trap group as an essential component. A radical trap group is a group that traps an active radical and stops a radical reaction. As such a group, a group that reacts with an active radical and is converted into a stable free radical and a group that has a stable free radical Is mentioned. Examples of such a structure having no basicity and having a radical trap group include hindered phenol groups, hydroquinone groups, N-oxyl free radical groups, nitroso groups, and nitrone groups.
The number of radical trap groups that compound RT has is not particularly limited, but when RT is a polymer compound having a repeating unit, the repeating unit having a radical trap group has 1 to 5 radical trap groups, In particular, it is preferable to have 1 to 3 repeating units. Moreover, it is preferable that the composition ratio of the repeating unit which has a radical trap group in the said high molecular compound is 1-100 mol%, 10-100 mol% is more preferable, 30-100 mol% is especially preferable. When the compound RT is a compound other than the above polymer compound, the radical trap group preferably has 1 to 10 radical trap groups in one molecule, more preferably 1 to 5, and preferably 1 to 3. Is particularly preferred.

  The radical trap group is particularly preferably a group having a nitrogen-oxygen bond, and groups represented by any one of the following general formulas (1) to (3) (in order, N-oxyl free radical group, nitroso group, nitrone group, respectively) ) Is more preferable.

In the general formula, R _{1 to} R ₆ each independently represents an alkyl group, a cycloalkyl group, or an aryl group. In Formula (1), R ₁ and R ₂ may be bonded to form a ring, and in Formula (3), at least two of R _{4 to} R ₆ may be bonded to form a ring.
An alkyl group, a cycloalkyl group or an aryl group as R _{1 to} R ₆ , a ring that R ₁ and R ₂ may be bonded to each other, and at least two of R _{4 to} R ₆ may be bonded to each other. A good ring may have a substituent.
The alkyl group as R _{1 to} R ₆ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, ethyl group, n-propyl group, i-propyl group, n- A butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group and the like can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are preferable.
The cycloalkyl group as R _{1 to} R ₆ preferably has 3 to 15 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl and the like.
The aryl group as R _{1 to} R ₆ preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
The ring that R ₁ and R ₂ may form and the ring that R _{4 to} R ₆ may form are preferably 5 to 10 membered rings, more preferably 5 or 6 membered rings.

As R _{1 to} R ₆ , an alkyl group, a cycloalkyl group, an aryl group, a ring that may be formed by combining R ₁ and R ₂ , and a ring that may be formed by combining R _{4 to} R ₆ As the substituent that may have, a halogen atom (for example, fluorine atom), hydroxyl group, carboxyl group, cyano group, nitro group, amino group, oxy group, alkoxy group, alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group, an acylamido group (RCONH-: R is a substituted or unsubstituted alkyl group or a phenyl _{group), - SO 2 Na, -P} (= O) (OC 2 H 5) 2, etc. and the like it can. Examples of the substituent that the cycloalkyl group or aryl group as R _{1 to} R ₆ may have further include an alkyl group.
Further, the compound represented by any one of the general formulas (1) to (3) may be in the form of a resin, and at least one of R _{1 to} R ₆ is bonded to the main chain or side chain of the resin. It may be.
The molecular weight of the compound (C) is not particularly limited, and is preferably a molecular weight of 100 to 5000, more preferably 100 to 2000, and particularly preferably 100 to 1000.

  Specific examples of the compound having a radical trap group are shown below, but the present invention is not limited thereto.

As the compound having a radical trap group, a commercially available product may be used, or a compound synthesized by a known method may be used. A compound having a radical trap group on a polymer is a low molecular compound having a commercially available radical trap group and a polymer having a reactive group such as an epoxy group, a halogenated alkyl group, an acid halide group, a carboxyl group, or an isocyanate group. It can be synthesized by a polymer reaction with a compound.
The usage-amount of the compound which has a radical trap group is 0.001-10 mass% normally on the basis of the total solid of the composition of this invention, Preferably it is 0.01-5 mass%.

[4] Hydrophobic resin When a film comprising an actinic ray-sensitive or radiation-sensitive resin composition is exposed through an immersion medium, a hydrophobic resin (HR) may be added as necessary. it can. As a result, hydrophobic resin (HR) is unevenly distributed on the surface layer of the actinic ray-sensitive or radiation-sensitive resin composition, and when the immersion medium is water, the receding contact angle of the film surface with respect to water is improved. And immersion water followability can be improved. As the hydrophobic resin (HR), any resin can be used as long as the receding contact angle of the surface can be improved by addition, but a resin having at least one of fluorine atom and silicon atom is preferable. The receding contact angle of the actinic ray-sensitive or radiation-sensitive resin composition film is preferably 60 ° to 90 °, more preferably 70 ° or more. The addition amount can be adjusted as appropriate so that the receding contact angle of the film falls within the above range, but is 0.1 to 10% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is preferable that it is 0.1 to 5% by mass. Hydrophobic resin (HR) is unevenly distributed at the interface as described above, but unlike surfactants, 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

The receding contact angle is the contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of droplet movement under dynamic conditions. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.
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. The contact angle of the immersion liquid with respect to the film in the film becomes important, and the performance of following the high-speed scanning of the exposure head is required without droplets remaining.

  The fluorine atom or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin or may be substituted on the side chain.

The hydrophobic resin (HR) is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and the aryl group may further have another substituent.

  Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The present invention is not limited to this.

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 , R _{62 to} R ₆₄ and R _{65 to} R ₆₈ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably having a carbon number of 1 ~ 4). 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 (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 1,3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.

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

The hydrophobic resin (HR) is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. As the divalent linking group, an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a group selected from the group consisting of a ureylene group or two or more groups. A combination is mentioned.
n represents an integer of 1 to 5.

Hereinafter, although the specific example of the repeating unit which has group represented by general formula (CS-1)-(CS-3) is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Furthermore, the hydrophobic resin (HR) may have a group that improves the affinity for water in the presence of a base. There is no particular limitation on the group that improves the affinity for water in the presence of a base,
(X) a group having an active proton,
(Y) A group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer.
(x) The group having an active proton is preferably a group having a pKa of 15 or less. Examples of the group having an active proton include a phenolic hydroxyl group, a carboxylic acid group, an aliphatic alcohol substituted with an electron withdrawing group at the α-position (for example, hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, and a sulfonylimide group. , (Alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkyl Examples include a sulfonyl) imide group, a tris (alkylcarbonyl) methylene group, and a tris (alkylsulfonyl) methylene group.
(x) The repeating unit having a group having an active proton 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 of acrylic acid or methacrylic acid, or a resin via a linking group. Examples include repeating units in which an alkali-soluble group is bonded to the main chain, and further, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be introduced at the end of the polymer chain at the time of polymerization. This is also preferable.

Specific examples of such repeating units are shown below, but are not limited thereto. Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

Furthermore, the specific example of the monomer which provides the repeating unit which has group which has an active proton is shown. In specific examples, Y represents a hydrogen atom, and R ₃ represents a hydrogen atom or a methyl group.

  The content of the repeating unit having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the polymer.

(Y) Groups that decompose by the action of an alkali developer and increase the solubility in an alkali developer include, for example, an active carboxylic acid ester group, a group having a lactone structure, an acid anhydride group, an acid imide group, and a carbonate ester. Groups, sulfate ester groups, sulfonate ester groups, etc. (wherein the active carboxylate ester group is an ester obtained from an alcohol having a pKa of 13 or less, such as phenol, thiol α-position is substituted with an electron withdrawing group. It represents an ester such as an aliphatic alcohol (for example, hexafluoroisopropanol group). A group having a lactone structure is preferred.
As the repeating unit having a group (y) that is decomposed by the action of an alkali developer and increases the solubility in the alkali developer, an alkali is added to the main chain of the resin, such as a repeating unit of an acrylate ester or a methacrylate ester. A polymerization initiator having a repeating unit to which a group (y) that decomposes by the action of the developer and increases the solubility in an alkali developer is bonded, or a group (y) that increases the solubility in an alkali developer And a chain transfer agent used at the time of polymerization are preferably introduced at the end of the polymer chain.
Further, the hydrophobic resin (HR) contains at least one of the structures represented by the following general formulas (2) to (4) as a repeating unit having a group that improves the affinity for water in the presence of a base. It is preferable.

In the general formulas (2) to (4), each R ₁ independently represents a hydrogen atom, a fluorine atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. R ₂ represents a hydrogen atom, —R ₃ —CO ₂ H or —R ₃ —OH. R ₃ represents a divalent organic group which may contain fluorine. R ₄ represents a methylene group, an oxygen atom or a sulfur atom. R ₅ represents a hydrogen atom, a linear or branched alkyl group, or —CO ₂ R ₇ . R ₆ is a hydrogen atom, a linear or branched alkyl group, a cyano group, or —CO ₂ R ₇ . R ₇ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group. R _8a and R _8b each independently represent a single bond, a linear or branched alkylene group having 1 to 4 carbon atoms, or a cycloalkylene group. The above substituent may further have a substituent.

  In addition, a repeating unit represented by the formula (K0) can be given.

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

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

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

  In addition, as described above, the ester group directly connected to the main chain of the repeating unit represented by the general formula (K0) is not included in the polar conversion group in the present invention.

  The polar conversion group is preferably a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH—, Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.

Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.

The repeating unit (c) has a group having a partial structure represented by the general formula (KA-1) or (KB-1), and thus has a preferred polarity conversion group, but the general formula (KA-1 In the case where the partial structure does not have a bond as in the case of the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent, The group having a partial structure is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the partial structure. The partial structure represented by the general formula (KA-1) or (KB-1) is linked to the main chain of the resin (C) through a substituent at an arbitrary position.

  The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure with the group as X.

  X in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, or a carbonic acid ester group. More preferably, it is a carboxylic acid ester group.

The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .

Z _ka1 independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group, when there are a plurality of them.

Z _ka1 may be linked to form a ring. Examples of the ring formed by linking Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (such as a cyclic ether ring and a lactone ring).

  nka represents an integer of 0 to 10. Preferably it is an integer of 0 to 8, more preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

The electron withdrawing group as Z _{ka1 is the same} as the electron withdrawing group as Y ¹ and Y ² described later.

  The electron withdrawing group may be substituted with another electron withdrawing group.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron withdrawing group, and more preferably an alkyl group, a cycloalkyl group, or an electron withdrawing group. In addition, as an ether group, the thing substituted by the alkyl group or the cycloalkyl group, ie, the alkyl ether group, etc. are preferable. The electron withdrawing group has the same meaning as described above.

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

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

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

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

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

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

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

  In addition, as in the following (KA-1-1) to (KA-1-17), a 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1) has a bicyclo structure, a spiro It is preferred that other ring structures are condensed in a form that forms the structure.

  As for the peripheral ring structure to which the ring structure represented by the general formula (KA-1) may be bonded, for example, those in the following (KA-1-1) to (KA-1-17), or The thing according to can be mentioned.

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

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

Some lactone structures have optically active substances, but any optically active substance may be used. One optically active substance may be used alone or a plurality of optically active substances may be mixed and used. When one kind of optically active substance is mainly used, the optical purity (ee) is preferably 90 or more, more preferably 95 or more, and most preferably 98 or more.

  Preferred examples of X in the general formula (KB-1) include a carboxylic acid ester group (—COO—).

Y ¹ and Y ² in formula (KB-1) each independently represent an electron-withdrawing group.

  The electron withdrawing group is a partial structure represented by the following formula (EW). * In the formula (EW) represents a bond directly connected to (KA-1) or a bond directly connected to X in (KB-1).

In formula (EW),
n _ew is the number of repeating linking groups represented by —C (R _ew1 ) (R _ew2 ) — and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond, indicating that Y _ew1 is directly bonded.
Y _ew1 represents a halogen atom, a cyano group, a nitrile group, a nitro group, —C (R _f1 ) (R _f2 ) —
Examples thereof include a halo (cyclo) alkyl group represented by R _f3 , a haloaryl group, an oxy group, a carbonyl group, a sulfonyl group, a sulfinyl group, and combinations thereof. The electron-withdrawing group has, for example, the following structure: Also good. The “halo (cyclo) alkyl group” represents an alkyl group or a cycloalkyl group that is at least partially halogenated. R _ew3 and R _ew4 each independently represent an arbitrary structure. R _ew3 and R _ew4 may have any structure, and the partial structure represented by the formula (EW) may have an electron withdrawing property, and may be linked to, for example, the main chain of the resin. An alkyl group and a fluorinated alkyl group;

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

At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.

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

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

R _{f1 to} R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.

Examples of the (halo) alkyl group in R _{f1 to} R _f3 include the alkyl group in Z _ka1 described above and a structure in which this is halogenated.

Examples of the (per) halocycloalkyl group and (per) haloaryl group in R _{f1 to} R _f3 or in the ring formed by linking R _f2 and R _f3 include the above-described cycloalkyl group in Z _ka1 is halogen. phased structure, more preferably _{-C (n) F (2n-} 2) fluoroalkyl group represented by H, and include perfluoro aryl group represented by _{-C (n) F (n-} 1) It is done. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.

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

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

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

  Even if the repeating unit (c) is a repeating unit (c ′) having at least one of a fluorine atom and a silicon atom and a polarity converting group on one side chain, it has a polarity converting group, and Even a repeating unit (c *) having no fluorine atom and silicon atom has a polarity converting group on one side chain, and on a side chain different from the side chain in the same repeating unit, Although it may be a repeating unit (c ″) having at least one of a fluorine atom and a silicon atom, the resin (C) more preferably has a repeating unit (c ′) as the repeating unit (c).

  In addition, when resin (C) has a repeating unit (c *), it is preferable that it is a copolymer with the repeating unit (repeating unit (c1) mentioned later) which has at least any one of a fluorine atom and a silicon atom. In the repeating unit (c ″), the side chain having a polarity converting group and the side chain having at least one of a fluorine atom and a silicon atom are bonded to the same carbon atom in the main chain. It is preferable to have a positional relationship as shown in Formula 4. In the formula, B1 represents a partial structure having a polar conversion group, and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

  In the repeating unit (c *) and the repeating unit (c ″), the polar conversion group is more preferably a partial structure represented by —COO— in the structure represented by the general formula (KA-1).

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

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

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

  The hydrolysis rate of the resin (C) with respect to the alkaline developer is preferably 0.001 nm / sec or more, more preferably 0.01 nm / sec or more, and further preferably 0.1 nm / sec or more. Most preferably, it is 1 nm / sec or more.

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

  The resin (C) of the present invention is preferably a resin (C1) containing a repeating unit (c) having at least two or more polar conversion groups and having at least one of a fluorine atom and a silicon atom. .

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

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

R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include the same groups as Y ₁ and Y ₂ in the formula (KB-1), preferably a halogen atom or —C (R _f1 ) (R _f2 ) —R _f3 . It is a halo (cyclo) alkyl group or a haloaryl group represented. Preferably R _ky3 halogen atom, or, -C (R _f1) (R _f2) halo (cyclo) alkyl groups or haloaryl groups represented by -R _f3, lactone ring R _ky2 is linked to R _ky1 Or an electron withdrawing group having no halogen atom.

R _ky1 , R _ky2 and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.

Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka1 in formula (KA-1).

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

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

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

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

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

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

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

In formula (KY-3),
Z _ka1 and nka each have the same meaning as in the general formula (KA-1). R _ky5 is synonymous with the formula (KY-2).
L _ky represents an alkylene group, an oxygen atom or a sulfur atom. _Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

The repeating unit (c) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation, etc., but is a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Preferably there is. Examples include acrylate-based repeating units (including those having substituents at the α-position and β-position), styrene-based repeating units (including those having substituents at the α-position and β-position), vinyl ether-based repeating units, norbornene-based Repeating units, maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), and the like, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units An acrylate-based repeating unit, a vinyl ether-based repeating unit, and a norbornene-based repeating unit are more preferable, and an acrylate-based repeating unit is most preferable.
The repeating unit (c) may be a repeating unit having the partial structure shown below.

In general formula (cc),
Z ₁ each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and preferably represents an ester bond.
Z ₂ each independently represents a chain or cyclic alkylene group, preferably an alkylene group having 1 or 2 carbon atoms or a cycloalkylene group having 5 to 10 carbon atoms.
Ta independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group, or an electron withdrawing group (as Y ¹ and Y ² in the general formula (KB-1)). And preferably represents an alkyl group, a cycloalkyl group, or an electron withdrawing group, and more preferably represents an electron withdrawing group. When there are a plurality of Ta, Tas may be bonded to form a ring.

L ₀ represents a single bond or an m + 1 valent hydrocarbon group (preferably having 20 or less carbon atoms), and preferably represents a single bond. The single bond as L ₀ is when m is 1. The m + 1 valent hydrocarbon group as L ₀ represents, for example, an m + 1 valent hydrocarbon group obtained by removing m-1 arbitrary hydrogen atoms from an alkylene group, a cycloalkylene group, a phenylene group, or a combination thereof. . when k is 2, it may form a ring by bonding to each other two L _o.

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

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

m represents an integer of 0 to 28, preferably an integer of 1 to 3, and more preferably 1.
k represents an integer of 0 to 2, and is preferably 1.
q represents the integer of 0-5, Preferably it is 0-2.
r represents an integer of 0 to 5.
In addition, -L _0- (Ta) m may be substituted instead of-(L) r-Tc.
The case where the sugar lactone has a fluorine atom at the terminal and the case where the sugar lactone has a fluorine atom on a side chain different from the side chain on the sugar lactone side in the same repeating unit (repeating unit (c ")) are also preferable.

  The more specific structure of the repeating unit (c) is preferably a repeating unit having the partial structure shown below.

In general formulas (ca-2) and (cb-2),
Z ₁ , Z ₂ , Tc, Ta, L, q and r have the same meanings as in the general formula (cc).

Tb independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group, or an electron withdrawing group (as Y ¹ and Y ² in the general formula (KB-1)). It is synonymous with the electron withdrawing group.

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

  m represents an integer of 1 to 28, preferably an integer of 1 to 3, and more preferably 1.

n represents an integer of 0 to 11, preferably an integer of 0 to 5, and more preferably 1 or 2.
p represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.

In general formula (2),
R ₂ represents a chain or cyclic alkylene group, and when there are a plurality of R ₂ groups, they may be the same or different.
R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbons are substituted with fluorine atoms.
R ₄ is a halogen atom, cyano group, hydroxy group, amide group, alkyl group, cycloalkyl group, alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). When there are a plurality of R _{4 s} , they may be the same or different, and two or more R ₄ may be bonded to form a ring.

X represents an alkylene group, an oxygen atom, or a sulfur atom.
Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.
* Represents a bond to the main chain of the resin.
n represents the number of repetitions and represents an integer of 0 to 5.
m is the number of substituents and represents an integer of 0 to 7.
The structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) ₁ —COO— (l represents an integer of 1 to 5).
Specific examples of the repeating unit having a group that improves the affinity for water in the presence of a base are shown below.
Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

In the formula, R ^1b represents a hydrogen atom, a fluorine atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. The alkyl group may have a fluorine atom or a hydroxy group as a substituent. R ⁷ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group. The alkyl group and cycloalkyl group as R ⁷ may each have a fluorine atom as a substituent.

The content of the repeating unit having a group (y) whose solubility in an alkali developer is increased is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, still more preferably based on all repeating units in the polymer. 5 to 15 mol%.
The content of the repeating unit having a group that improves the affinity for water in the presence of a base is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, and still more preferably 5 to 5 mol%, based on all repeating units in the polymer. 20 mol%.

The hydrophobic resin (HR) may further have (z) a group that decomposes by the action of an acid.
In the hydrophobic resin (HR), the repeating unit having a group (z) that is decomposed by the action of an acid is the same as the repeating unit having an acid-decomposable group listed for the resin of the component (B), Specific examples are given below.

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

The hydrophobic resin (HR) may further have a repeating unit represented by the following general formula (CIII).

In general formula (CIII):
R _c31 represents a hydrogen atom, an alkyl group _optionally substituted with a fluorine atom, a cyano group, or —
It represents a CH ₂ -O-Rac ₂ group. Wherein, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group. These groups may be substituted with a fluorine atom or a silicon atom.
L _c3 represents a single bond or a divalent linking group.

In general formula (CIII), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an ester group, an alkylene group (preferably having a carbon number of 1 to 5), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).

When the hydrophobic resin (HR) has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass, and preferably 10 to 80% by mass with respect to the molecular weight of the hydrophobic resin (HRC). Is more preferable. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% in hydrophobic resin (HR), and it is more preferable that it is 30-100 mass%.
When the hydrophobic resin (HR) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass, and 2 to 30% by mass with respect to the molecular weight of the hydrophobic resin (HR). Is more preferable. Moreover, it is preferable that it is 10-100 mass% in a hydrophobic resin (HR), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-100 mass%.

  The weight average molecular weight of the hydrophobic resin (HR) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. is there.

  The hydrophobic resin (HR), like the resin (B), naturally has few impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably 0. -5 mass%, 0-1 mass% is still more preferable. As a result, an actinic ray-sensitive or radiation-sensitive resin composition that does not change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably 1 in terms of resolution, pattern shape, pattern sidewall, roughness, and the like. It is the range of ~ 2.

  In the case where the hydrophobic resin (HR) is commercially available, various commercially available products can be used, and in the same manner as the resin (B) described above, it can be synthesized and purified according to a conventional method (for example, radical polymerization). .

  Specific examples of the hydrophobic resin (HR) are shown below. Table 1 below shows the molar ratio of the 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.

  Resin (C) can be used individually by 1 type or in combination of 2 or more types.

[5] Solvent Examples of the solvent that can be used in preparing the composition of the present invention by dissolving the above components include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, Organic solvents such as alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may contain rings (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, etc. Can be mentioned.

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

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

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, -Penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcyclo A preferred example is heptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
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 a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid -2- (2-ethoxyethoxy) ethyl and propylene carbonate are mentioned.
In the present invention, the above solvents may be used alone or in combination of two or more.

  In the present invention, it is preferable not to use a protic solvent containing a hydroxyl group or the like in the structure as the organic solvent, but a mixed solvent in which a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group are used may be used. Good.

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

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

  The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 0/100 to 99/1, preferably 0/100 to 80/20, more preferably 0/100 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

[6] Basic compound The composition of the present invention preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

  About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.

  The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

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

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undecar 7-ene etc. are mentioned. Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris ( and t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. As the compound having an onium carboxylate structure, an anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

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

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably C6-C12) may be bonded to a nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group. Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. As the halogen atom, chloride, bromide, and iodide are particularly preferable. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Etc. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be any in the range of 1 to 5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

In the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group, the sulfonic acid ester group includes an alkyl sulfonic acid ester,
Either cycloalkyl group sulfonate ester or aryl sulfonate ester may be used. In the case of alkyl sulfonate ester, the alkyl group has 1 to 20 carbon atoms, and in the case of cycloalkyl sulfonate ester, the cycloalkyl group has 3 carbon atoms. In the case of -20 and aryl sulfonate ester, the aryl group preferably has 6 to 12 carbon atoms. Alkyl sulfonic acid ester, cycloalkyl sulfonic acid ester, and aryl sulfonic acid ester may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, and a sulfonic acid. An ester group is preferred.

It is preferable to have at least one oxyalkylene group between the sulfonate group and the nitrogen atom. The number of oxyalkylene groups is 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.
These basic compounds are used alone or in combination of two or more.

  The usage-amount of a basic compound is 0-10 mass% normally based on solid content of the composition of this invention, Preferably it is 0-5 mass%.

  The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

[7] Surfactant The composition of the present invention may further contain a surfactant. As the surfactant, any one of fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, surfactant having both fluorine atom and silicon atom), or two or more kinds thereof Is preferred.

  When the composition of the present invention contains the above-mentioned surfactant, it is possible to give a pattern with less adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. Become.

  Examples of the fluorine-based and / or silicon-based surfactant include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, JP 2002-277862 A, US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, 5,824,451 Surfactant can be mentioned, The following commercially available surfactant can also be used as it is.

Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.),
Megafuck F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink and Chemicals), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass ( Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toagosei Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF801, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-18204, FTX-18204 230G, 2 4D, may be mentioned 208D, 212D, 218D, the fluorine-based surfactant or silicone-based surfactants such as 222D ((KK) Neos). Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

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

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

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₃ F ₇ group and (poly (oxy And a copolymer of (ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate).

In the present invention, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Sorbitans such as polyoxyethylene alkyl aryl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopa Mite - DOO, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, may be mentioned polyoxyethylene sorbitan tristearate nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as such.
These surfactants may be used alone or in several combinations.
The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, particularly preferably based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). Is 0.0005 to 1 mass%.

[8] Carboxylic acid onium salt The composition of the present invention may contain a carboxylic acid onium salt. Examples of the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt. In particular, as the carboxylic acid onium salt, an iodonium salt and a sulfonium salt are preferable. Furthermore, it is preferable that the carboxylate residue of the carboxylic acid onium salt of the present invention does not contain an aromatic group or a carbon-carbon double bond. As a particularly preferable anion moiety, a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.

  Fluorine-substituted carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, 2 , 2-bistrifluoromethylpropionic acid anion and the like.

These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

  The content of the carboxylic acid onium salt in the composition is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass, based on the total solid content of the composition. %.

[9] Dissolution-inhibiting compound The composition of the present invention comprises a dissolution-inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “dissolution-inhibiting compound”), which decomposes by the action of an acid and increases the solubility in an alkaline developer. You may contain. As a dissolution inhibiting compound, a fat containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996) is used because it does not lower the permeability below 220 nm. Cyclic or aliphatic compounds are preferred. Examples of the acid-decomposable group and alicyclic structure are the same as those described for the component (B) resin.

  When the composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.

The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.
The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the solid content of the composition of the present invention.
Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

[10] Other additives In the composition of the present invention, if necessary, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer (for example, a molecular weight of 1000 or less) A phenol compound, an alicyclic compound having a carboxyl group, or an aliphatic compound).

  Such a phenol compound having a molecular weight of 1000 or less is disclosed in, for example, JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. It can be easily synthesized by those skilled in the art with reference to the method described.

  Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

[11] Pattern Forming Method The composition of the present invention is preferably used at a film thickness of 30 to 250 nm, more preferably at a film thickness of 30 to 200 nm, from the viewpoint of improving resolution. By setting the solid content concentration in the actinic ray-sensitive or radiation-sensitive resin composition to an appropriate range to have an appropriate viscosity, and improving the coating property and film forming property, such a film thickness is obtained. Can do.
The total solid concentration in the actinic ray-sensitive or radiation-sensitive resin composition is generally 1 to 10% by mass, more preferably 1 to 8.0% by mass, and still more preferably 1.0 to 6.0. % By mass.

  The composition of the present invention is used by dissolving the above-described components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and applying the solution on a predetermined support as follows. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon.

For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater. Dry to form a 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.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., preferably 250 nm or less, more preferably 220 nm or less, particularly Preferably, far ultraviolet light having a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, electron beam, etc., ArF excimer Laser, F ₂ excimer laser, EUV (13 nm), and electron beam are preferable.

An antireflective film may be coated on the substrate in advance before forming a film comprising the actinic ray-sensitive or radiation-sensitive resin composition.
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.

  In the development step, an alkaline developer is used as follows. Examples of the alkali developer for the actinic ray-sensitive or radiation-sensitive resin composition include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, and n-propyl. Primary amines such as amines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxy Alkaline aqueous solutions such as quaternary ammonium salts such as tetraethylammonium hydroxide and cyclic amines such as pyrrole and pihelidine can be used.

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

  Further, after the development process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

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 performance required for the top coat and how to use it are explained in Chapter 7 of "Category and process of immersion lithography" published by CMMC.
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 thereof include a polymer and a fluorine-containing polymer. The aforementioned hydrophobic resin (HR) is also suitable as a top coat. Commercially available top coat materials can also be used as appropriate. 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

<ArF exposure evaluation>
<Synthesis of Resin RA-1>
Under a nitrogen stream, 57.59 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. To this, 12.42 g of compound X, 11.11 g of compound Y, 5.51 g of compound Z, and 1.43 g of initiator V-601 (5.0 mol% based on the monomer, manufactured by Wako Pure Chemical Industries) were converted to 98.84 g of cyclohexanone. The dissolved solution was added dropwise over 6 hours. After completion of dropping, the reaction was further continued at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixed solution of 900 ml of methanol / 100 ml of water over 20 minutes. The precipitated powder was collected by filtration and dried to obtain 18 g of Resin (RA-1). The weight average molecular weight of the obtained resin was 13700 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.89.

  Other resins (RA-2 to RA-10) were synthesized using the same method. The weight average molecular weight was prepared by changing the amount of initiator.

<Synthesis of p- (1- (cyclohexylethoxy) ethoxy) styrene / p-hydroxystyrene (40/60) (resin RA-11)>
70 g of p-hydroxystyrene (Nippon Soda VP-8000) was dissolved in 320 g of propylene glycol monomethyl ether acetate (PGMEA), dehydrated by distillation under reduced pressure, and then cooled to 20 ° C. Thereto, 41.4 g of cyclohexyl vinyl ether was added and stirred, and 100 mg of p-toluenesulfonic acid was added and reacted for 3 hours.
To the reaction solution, 0.28 g of triethylamine and 320 ml of ethyl acetate were added, and this was washed 3 times with 150 ml of distilled water. The solvent was distilled off and concentrated. The obtained oil was dissolved in 100 ml of acetone, and this was slowly poured into 2 L of distilled water. The precipitated powder was collected by filtration and dried to obtain 54 g of the desired product. (Weight average molecular weight 10,000, dispersity 1.30)

  The repeating unit (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) in each resin are shown below.

Synthesis example of PAG-1

Synthesis of Compound A A 100 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was charged with 2.32 g (16.7 mmol) of decahydroisoquinoline, 1.69 g (16.7 mmol) of triethylamine and 30 g of chloroform. From the dropping funnel, 3.00 g (16.7 mmol) of 2- (fluorosulfonyl) difluoroacetyl fluoride was added dropwise while maintaining the temperature at 20 to 35 ° C. After the addition, the reaction solution was continuously stirred at around room temperature for 1 hour. 30 g of water was added to the reaction solution to separate the organic layer. This washing operation was further performed twice, and then the organic layer was concentrated to obtain 5.84 g of a reaction mixture. This reaction mixture was purified by a 15 g silica gel column using hexane: ethyl acetate = 5: 1 (volume ratio) as a developing solution. After removing the solvent under reduced pressure, 3.25 g (10.8 mmol) of compound A was obtained in 65.2% yield.

Synthesis of Compound B Compound A3.00 g (10.0 mmol) and THF 50 g were charged into a 100 mL four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer. From a dropping funnel, a solution of 10.2 g (100 mmol) of triethylamine and 1.49 g (10.0 mmol) of trifluoromethanesulfonamide in 50 g of THF was added dropwise, and after addition, the reaction solution was stirred at 80 ° C. for 6 hours. To this reaction solution, 50 g of dichloromethane and 50 g of 1N hydrochloric acid were added to separate the organic layer. This organic layer was washed with 50 g of 1N aqueous sodium hydroxide and 50 g of water and then concentrated to obtain 6.2 g of a crude product. This crude product was used for the next reaction without purification.

Synthesis of PAG1 1.40 g (10.0 mmol) of 1- (cyclohexylmethoxy) naphthalene was dissolved in 15 g of Eaton reagent in a three-necked flask, and then tetramethylene sulfoxide 1.04 with stirring.
g (10.0 mmol) was added dropwise, and the mixture was further stirred for 3 hours. The reaction solution was poured into 100 g of water, and then 6.2 g of the composition product of Compound B and 50 g of chloroform were added. After separating the organic layer, the aqueous layer was further extracted twice with 50 g of chloroform. The obtained organic layers were combined, washed twice with water and concentrated. The resulting compositional organism was recrystallized from 10 g of ethyl acetate to obtain 4.17 g (5.53 mmol, 55.3%) of PAG1.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in Table 2 below are dissolved in a solvent, and a solution with a solid concentration of 5% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.03 μm, and actinic ray sensitive or radiation sensitive. A resin composition (corresponding to a positive resist composition) was prepared. The prepared composition was evaluated by the following method, and the results are shown in Table 2. About each component in Table 2, the ratio at the time of using multiple is a mass ratio.

Compounds having radical trap groups (radical trapping agents)

  Hereinafter, abbreviations in the table are shown.

〔solvent〕
S1: Propylene glycol methyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane)
S2: 2-Heptanone
S3: cyclohexanone
S4: γ-butyrolactone
S5: Propylene glycol methyl ether (PGME: 1-methoxy-2-propanol)
[Surfactant]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
[Basic compounds]
D-1: Triphenylsulfonium acetate
D-2: 2,6-Diisopropylaniline D-3: Triethanolamine

<Evaluation>
(Exposure conditions (1) ArF dry exposure: Example 1)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. The prepared positive composition was applied thereon and baked at 130 ° C. for 60 seconds to form a 120 nm thick film. Using the obtained wafer ArF excimer laser scanner (manufactured by ASML, PAS5500 / 1100, NA0.75), exposure was performed through a 6% halftone mask of 75 nm 1: 1 line and space pattern. After heating at 130 ° C. for 60 seconds, the film was developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsed with pure water, and then spin-dried to obtain a pattern.

[Exposure latitude]
The exposure amount that reproduces a mask pattern of 75 nm 1: 1 line and space is set as the optimal exposure amount, and when the exposure amount is changed, an exposure amount width that allows a pattern size of 75 nm ± 10% is obtained, and this value is determined as the optimal exposure amount. Divided by the amount and expressed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

[Line edge roughness]
For the measurement of line edge edge roughness, a length measuring SEM (Hitachi, Ltd. S-9260) is used to observe an isolated pattern of 75 nm at an optimum exposure amount, and the edge of the line pattern in the longitudinal direction is 5 μm. The distance from the reference line that should have an edge was measured at 50 points, the standard deviation was obtained, and 3σ was calculated. A smaller value indicates better performance.

[Development defects]
Using a defect inspection device KLA2360 (trade name) manufactured by KLA-Tencor Corporation, the pixel size of the defect inspection device is set to 0.16 μm, the threshold value is set to 20, and measurement is performed in a random mode. And the number of development defects per unit area (cm ² ) was calculated. The value is 0
. A sample having a value of less than 5 was evaluated as “◯”, a value of 0.5 or more and less than 0.8 as “Δ”, and a value of 0.8 or more as “x”. A smaller value indicates better performance.
[Profile]
An isolated pattern of 85 nm was observed using a scanning electron microscope.

(Exposure condition (2) ArF immersion exposure: Examples 2 to 12 and Comparative Examples 1 to 3)
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 prepared positive composition was applied thereon and baked at 130 ° C. for 60 seconds to form a 120 nm thick film. The obtained wafer was used with an ArF excimer laser immersion scanner (manufactured by ASML, XT1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection), 6% half of 65 nm 1: 1 line and space pattern Exposed through tone mask. Ultra pure water was used as the immersion liquid. After heating at 130 ° C. for 60 seconds, the film was developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsed with pure water, and then spin-dried to obtain a pattern.

[Exposure latitude]
The exposure amount that reproduces a 65 nm 1: 1 line and space mask pattern is the optimum exposure amount, and when the exposure amount is changed, an exposure amount width that allows a pattern size of 65 nm ± 10% is obtained, and this value is the optimum exposure amount. Divided by the amount and expressed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

[Line edge roughness]
The line edge edge roughness is measured using a length measuring SEM (Hitachi, Ltd. S-9260) to observe an isolated pattern of 65 nm at the optimum exposure amount, and the edge of the line pattern in the longitudinal direction is 5 μm. The distance from the reference line that should have an edge was measured at 50 points, the standard deviation was obtained, and 3σ was calculated. A smaller value indicates better performance.

[Development defects]
Using a defect inspection device KLA2360 (trade name) manufactured by KLA-Tencor Corporation, the pixel size of the defect inspection device is set to 0.16 μm, the threshold value is set to 20, and measurement is performed in a random mode. And the number of development defects per unit area (cm ² ) was calculated. The value is 0
. A sample having a value of less than 5 was evaluated as “◯”, a value of 0.5 or more and less than 0.8 as “Δ”, and a value of 0.8 or more as “x”. A smaller value indicates better performance.

From the above evaluation results, by using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, development defects are suppressed in both normal exposure and immersion exposure, and the pattern is excellent in exposure latitude and line edge roughness. It was found that can provide.
[Profile]
An isolated pattern of 85 nm was observed using a scanning electron microscope.

<KrF exposure evaluation>
(1) Preparation of actinic ray-sensitive or radiation-sensitive resin composition Each component shown in Table 3 below is dissolved in a solvent to prepare a solution having a solid content concentration of 14.5% by mass, and then the obtained solution is prepared. Microfiltration was performed with a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain an actinic ray-sensitive or radiation-sensitive resin composition.
Hereinafter, in Table 3, the addition amount (mass%) of each component other than the solvent (numerical value in parentheses in the table) means mass% relative to the solid content excluding the solvent. About a solvent, each mixing ratio (mass%) is represented.

The abbreviations in the table represent the compounds represented by the abbreviations.
<Resin>

(2) Formation and evaluation of positive pattern (KrF exposure)
Hexamethyldisilazane treatment was performed on an 8-inch wafer obtained by depositing SiN on a silicon substrate with a thickness of 100 nm using a spin coater ACT8 manufactured by Tokyo Electron. Thereafter, the positive composition was applied onto this film and baked at 90 ° C. for 90 seconds to obtain a film having an average film thickness of 600 nm.
The obtained film was subjected to pattern exposure using a KrF excimer laser scanner (PAS5500 / 850C manufactured by ASML, wavelength 248 nm, NA = 0.60, Sigma = 0.70). The reticle used at this time used a binary mask.
After exposure, it was baked at 110 ° C. for 60 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds, and dried. The obtained pattern was evaluated by the following method.

(2-1) Sensitivity The line width of the obtained pattern was observed with a scanning electron microscope (S-8840 manufactured by Hitachi, Ltd.), and a line having a line width of 180 nm (in the mask, line size = 170 nm, line: space = 1: Irradiation energy when resolving 1.2) was defined as sensitivity (Eopt).

(2-2) Exposure dose dependency (EL)
The line width with respect to the exposure amount is measured by the same method as described above, and the exposure amount that is ± 10% of the target size of 180 nm, that is, the line width of 162 nm and the line width of 198 nm is obtained. Dependency (EL) was calculated. Larger values indicate less exposure dose dependency and higher resolution.
[EL (%)] = [(exposure amount at which line width is 162 nm) − (exposure amount at which line width is 198 nm)] / (Eopt)

(2-3) LER evaluation In the sensitivity obtained in (2-1), the line pattern with a line width of 180 nm was observed with a scanning microscope (S8840 manufactured by Hitachi, Ltd.), and the range of 2 μm in the longitudinal direction of the line pattern was The distance from the reference line that should have an edge to the actual edge was measured at 50 points at equal intervals, and the standard deviation was calculated for these measured values, and 3σ was calculated. A smaller value indicates better performance.

(2-4) Defects A 0.18 μm pattern was exposed in 78 locations on the wafer surface with an exposure amount that provides a 180 nm pattern with a mask pattern of 180 nm mask size and 360 nm pitch. The number of development defects of the obtained patterned wafer was measured with KLA-2360 manufactured by KLA-Tencor Corporation. In this case, the inspection area was 205 cm ² in total, the pixel size was 0.25 μm, the threshold = 30, and the inspection light was visible light. A value obtained by dividing the obtained numerical value by the inspection area is evaluated as the number of defects (pieces / cm ² ). Eight or more were marked with x. A smaller value indicates better performance.

<EUV exposure evaluation>
(3) Formation and evaluation of positive pattern (EUV exposure)
The same composition as that used in the above (KrF exposure) except that the solid content concentration was changed to 5% by mass was applied on a silicon wafer subjected to hexamethyldisilazane treatment using a spin coater Mark8 manufactured by Tokyo Electron. The film was baked at 100 ° C. for 90 seconds to obtain a film having an average film thickness of 100 nm.
The obtained film was exposed using EUV light (wavelength 13 nm: EUVES, manufactured by RISO TRACK JAPAN), and further baked at 110 ° C. for 60 seconds. Thereafter, development was performed using an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution. While changing the exposure amount in a range of 0 to 20.0 mJ / cm 2 by 0.5 mJ / cm 2, the dissolution rate of the film in the developer at each exposure amount was measured to obtain a sensitivity curve.

(Sensitivity and resolution (dissolution contrast))
In this sensitivity curve, the exposure amount when the dissolution rate is saturated was taken as sensitivity, and the dissolution contrast (γ value) was calculated from the gradient of the linear portion of the sensitivity curve as an index of resolution. The larger the γ value, the better the dissolution contrast and the higher the resolution.

  The EUV exposure evaluation results are shown in the following table.

<EB exposure evaluation>

  (4) Formation and evaluation of positive pattern (electron beam (EB) exposure)

The same composition as that used in the above (2) (KrF exposure) except that the solid content concentration was changed to 8% by mass was applied to a hexamethyldisilazane-treated silicon wafer using a spin coater Mark8 manufactured by Tokyo Electron. And then baked at 100 ° C. for 90 seconds to obtain a film having an average film thickness of 300 nm.
The film was irradiated with an electron beam by using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). After irradiation, it was baked at 110 ° C. for 60 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried. The obtained pattern was evaluated by the following method.

(4-1) Sensitivity When the line width of the obtained pattern was observed with a scanning electron microscope (S-9260 manufactured by Hitachi, Ltd.) and a line with a line width of 150 nm (line: space = 1: 1) was resolved. Irradiation energy was taken as sensitivity.

(4-2) Resolving power evaluation In the case of resolving a line: space = 1: 1 pattern with the sensitivity obtained in (3-1), the minimum value of the line width of a resolvable line is the scanning electron. Observed with a microscope.

(4-3) LER evaluation In the sensitivity obtained in (4-1), a line pattern with a line width of 150 nm was observed with a scanning microscope (S9260 manufactured by Hitachi, Ltd.), and the range of 2 μm in the longitudinal direction of the line pattern was The distance from the reference line that should have an edge to the actual edge was measured at 50 points at regular intervals, the standard deviation was obtained, and 3σ was calculated. A smaller value indicates better performance.

  It turns out that the composition of this invention has the outstanding performance in said each evaluation.

Claims (10)

(A) a compound capable of generating an acid upon irradiation with actinic rays or radiation, (B) a resin capable of increasing the dissolution rate in an alkali developer by the action of an acid, and (C) an actinic ray containing a compound having a radical trap group A resin having a repeating unit represented by the following general formula (I) or (A), wherein the resin (B) has a dissolution rate increased in an alkaline developer by the action of the acid. And (C) the compound having a radical trap group is a compound having a nitrogen-oxygen bond, an actinic ray-sensitive or radiation-sensitive resin composition .

In general formula (I),
R ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a monovalent organic group.
R ₂ represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
In general formula (A), R ₀₁ , R ₀₂ and R ₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Ar ₁ represents an aromatic ring group. Note that R ₀₃ and Ar ₁ are alkylene groups, and they may be bonded to each other to form a 5-membered or 6-membered ring together with the —C—C— chain.
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 Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.   The resin (B) whose dissolution rate in an alkaline developer increases by the action of the acid has a repeating unit represented by the general formula (A). In the general formula (A), Y represents the following general formula The composition according to claim 1, which is a group represented by (B).

  Where L ₁ And L ₂ Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  M represents a single bond or a divalent linking group.
  Q represents an alkyl group, an alicyclic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. In addition, these alicyclic groups and aromatic ring groups may contain a hetero atom.
  Q, M, L ₁ At least two of them may be bonded to each other to form a 5-membered or 6-membered ring.   In the said general formula (B), group represented by-(MQ) is C5-C20 group, The composition of Claim 2 characterized by the above-mentioned.   The composition according to any one of claims 1 to 3, wherein the resin (B) whose rate of dissolution in an alkaline developer is increased by the action of an acid has a repeating unit having a lactone group.   (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation, (B) a resin capable of increasing the dissolution rate in an alkali developer by the action of an acid, and (C) an actinic ray containing a compound having a radical trap group Or a radiation-sensitive resin composition, wherein the resin (B) whose dissolution rate in an alkaline developer is increased by the action of an acid has a repeating unit having a lactone group, and the (C) radical trap group An actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound having a nitrogen-oxygen bond is included. The composition according to any one of claims 1 to 5, further comprising a hydrophobic resin. The composition according to any one of claims 1 to 6 , wherein the compound (C) having a radical trap group is a compound represented by any one of the following general formulas (1) to (3).

In the general formula, R _{1 to} R ₆ each independently represents an alkyl group, a cycloalkyl group, or an aryl group. In Formula (1), R ₁ and R ₂ may be bonded to form a ring, and in Formula (3), at least two of R _{4 to} R ₆ may be bonded to form a ring.   The composition according to claim 7, wherein the compound having the (C) radical trap group is a compound represented by the general formula (2).   The film | membrane formed with the composition in any one of Claims 1-8. A pattern forming method comprising: exposing and developing the film according to claim 9 .