JP5422357B2 - 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 used in semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and other photofabrication lithography processes, and The present invention relates to a pattern forming method using In particular, the present invention relates to a positive resist composition suitable for exposure with an immersion projection exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, and a pattern forming method using the same.

  Along with the miniaturization of semiconductor elements, the wavelength of the exposure light source and the numerical aperture (high NA) of the projection lens have increased, and the resolution between the projection lens and the sample has been increased with the aim of higher resolution by further shortening the wavelength. A so-called immersion method is known in which a liquid having a refractive index (hereinafter also referred to as “immersion liquid”) is used. The liquid immersion method is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. When exposed, the acid generator in the exposed area decomposes to generate an acid, and the acid generated in the exposure bake (PEB) is a reaction catalyst. Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.
The ArF excimer laser (193 nm) resist using this chemical amplification mechanism is becoming mainstream at present, but when immersion exposure is performed, the formed line pattern collapses and becomes a defect during device manufacturing. However, the problem of the pattern collapse and the line edge roughness where the pattern side wall is rough are still insufficient.

In addition, when a chemically amplified resist is applied to immersion exposure, the resist layer comes into contact with the immersion liquid during exposure, so that the resist layer is altered and components that adversely affect the immersion liquid are exuded from the resist layer. It has been pointed out to do. On the other hand, Patent Documents 1 to 4 describe examples in which exudation is suppressed by adding a resin containing silicon atoms or fluorine atoms.
In the immersion exposure process, when exposure is performed using a scanning immersion exposure machine, the exposure speed decreases unless the immersion liquid moves following the movement of the lens. Concerned about giving. In the case where the immersion liquid is water, it is desirable that the resist film be hydrophobic because the water followability is good.
Patent Document 5 describes that the resist pattern shape can be improved by using a specific norbornane lactone derivative.

  However, even when immersion exposure is performed using the above technique, there has been a further demand for further reducing the occurrence of development defects, scum, particles, and bubble defects called BLOB defects, and improving the pattern shape.

JP 2006-309245 A JP 2007-304537 A JP 2007-182488 A JP 2007-153982 A JP 2008-111103 A

  The object of the present invention is to improve the generation of line edge roughness and scum, to form a pattern with fewer development defects, to reduce the acid elution into the immersion liquid, and to follow the immersion liquid. Furthermore, it is to provide an actinic ray-sensitive or radiation-sensitive resin composition having good performances of particle suppression, pattern shape and bubble defect suppression, and a pattern forming method using the same.

As a result of intensive studies to solve the above problems, the present inventor has reached the present invention shown below.
The present invention has the following configuration.

一般式（ＫＡ−１）及び（ＫＢ−１）において、
Ｚ_ｋａは、アルキル基、シクロアルキル基、エーテル基、ヒドロキシル基、アミド基、アリール基、ラクトン環基、又は電子求引性基を表し、Ｚ_ｋａが複数存在する場合、複数のＺ_ｋａは同じでも異なっていてもよい。
Ｚ_ｋａ同士が連結して環を形成しても良い。
ｎｋａは０〜１０の整数を表す。
Ｘ_ｋｂ１、Ｘ_ｋｂ２は各々独立して電子求引性基である。
ｎｋｂ、ｎｋｂ’は各々独立して０又は１を表す。
Ｒ_ｋｂ１〜Ｒ_ｋｂ４は、各々独立して水素原子、アルキル基、シクロアルキル基、アリール基、又は電子求引性基を表し、Ｒ_ｋｂ１、Ｒ_ｋｂ２及びＸ_ｋｂ１の少なくとも２つが互いに連結して環を形成していてもよく、Ｒ_ｋｂ３、Ｒ_ｋｂ４及びＸ_ｋｂ２の少なくとも２つが互いに連結して環を形成していてもよい。
２．
繰り返し単位（ｃ）が、１つの側鎖上に、少なくとも２つ以上の極性変換基と、フッ素原子及び珪素原子の少なくともいずれかと、を有する繰り返し単位（ｃ’）であることを特徴とする上記１に記載の感活性光線性又は感放射線性樹脂組成物。 1.
A resin (A) whose solubility in an alkaline developer is increased by the action of an acid, and
Containing a repeating unit (c) having at least two polar conversion groups represented by —COO— in the structure represented by the general formula (KA-1) or (KB-1), and containing a fluorine atom and silicon An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (C) having at least one of atoms.

In general formulas (KA-1) and (KB-1),
Z _ka 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, if Z _ka there are a plurality, the plurality of Z _ka same But it can be different.
Z _ka may be linked together to form a ring.
nka represents an integer of 0 to 10.
X _kb1 and X _kb2 are each independently an electron withdrawing group.
nkb and nkb ′ each independently represents 0 or 1.
R _{kb1 to} R _kb4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group, and at least two of R _kb1 , R _kb2 and X _kb1 are connected to each other to form a ring _And at least two of R _kb3 , R _kb4 and X _kb2 may be connected to each other to form a ring.
2.
The repeating unit (c) is a repeating unit (c ′) having at least two or more polar conversion groups and at least one of a fluorine atom and a silicon atom on one side chain. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to 1.

一般式（ＫＹ−１）において、
Ｒ_ｋｙ１、Ｒ_ｋｙ４はそれぞれ独立して、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、カルボニル基、カルボニルオキシ基、オキシカルボニル基、エーテル基、ヒドロキシル基、シアノ基、アミド基、又はアリール基を表す。Ｒ_ｋｙ１、Ｒ_ｋｙ４が同一の原子と結合して二重結合を形成していてもよい。
Ｒ_ｋｙ２、Ｒ_ｋｙ３はそれぞれ独立して電子求引性基、又は、Ｒ_ｋｙ１とＲ_ｋｙ２が連結してラクトン環を形成するとともにＲ_ｋｙ３が電子求引性基である。
Ｒ_ｋｙ１、Ｒ_ｋｙ２及びＲ_ｋｙ４の少なくとも２つが互いに連結して単環又は多環構造を形成しても良い。
Ｒ_ｋｂ１〜Ｒ_ｋｂ４、ｎｋｂ、ｎｋｂ’は各々前記式（ＫＢ−１）におけるものと同義である。 3.
The repeating unit (c) is a repeating unit (c *) having at least two or more polar conversion groups and not having a fluorine atom and a silicon atom, and the resin (C) is further a fluorine atom and a silicon atom. 2. The actinic ray-sensitive or radiation-sensitive resin composition as described in 1 above, which comprises a repeating unit having at least one of the following.
4).
The repeating unit (c) has at least two or more polar conversion groups on one side chain, and at least any one of a fluorine atom and a silicon atom on a side chain different from the side chain in the same repeating unit. 2. The actinic ray-sensitive or radiation-sensitive resin composition as described in 1 above, which is a repeating unit (c ″) containing
5.
The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of 1 to 4 above, wherein the repeating unit (c) has a structure represented by the following general formula (KY-1).

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. R _ky1 and R _ky4 may be bonded to the same atom to form a double bond.
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.
At least two of R _ky1 , R _ky2 and R _ky4 may be linked to each other to form a monocyclic or polycyclic structure.
R _{kb1 to} R _kb4 , nkb, and nkb ′ are respectively synonymous with those in the formula (KB-1).

式（ＫＹ−２）中、
Ｒ_ｋｙ６〜Ｒ_ｋｙ１０は、各々独立して、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、カルボニル基、カルボニルオキシ基、オキシカルボニル基、エーテル基、ヒドロキシル基、シアノ基、アミド基、又はアリール基を表す。
Ｒ_ｋｙ６〜Ｒ_ｋｙ１０は、２つ以上が互いに連結して単環又は多環構造を形成しても良い。
Ｒ_ｋｙ５は電子求引性基を表す。
Ｒ_ｋｂ１、Ｒ_ｋｂ２、ｎｋｂは各々前記式（ＫＢ−１）におけるものと同義である。 6).
The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of 1 to 5 above, wherein the repeating unit (c) has a structure represented by the following general formula (KY-2).

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.
R _kb1 , R _kb2 and nkb have the same _meanings as those in formula (KB-1).

一般式（Ｆ２）〜（Ｆ４）中、
Ｒ_５７〜Ｒ_６８は、各々独立に、水素原子、フッ素原子、直鎖もしくは分岐アルキル基、又はアリール基を表す。但し、Ｒ_５７〜Ｒ_６１、Ｒ_６２〜Ｒ_６４及びＲ_６５〜Ｒ_６８のそれぞれにおいて、少なくとも１つは、フッ素原子又は少なくとも１つの水素原子がフッ素原子で置換されたアルキル基を表す。Ｒ_６２とＲ_６３は、互いに連結して環を形成してもよい。

一般式（ＣＳ−１）〜（ＣＳ−３）中、
Ｒ_１２〜Ｒ_２６は、各々独立に、直鎖もしくは分岐アルキル基又はシクロアルキル基を表す。
Ｌ_３〜Ｌ_５は、単結合又は２価の連結基を表す。
ｎは、１〜５の整数を表す。 7).
The above 1 to 6, wherein the resin (C) has at least one of the groups represented by the general formulas (F2) to (F4) and the general formulas (CS-1) to (CS-3) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, a linear or branched alkyl group, or an aryl group. _However, in each of _{R 57 ~R 61, R 62 ~R} 64 and _R 65 _{to R 68,} at least one represents a fluorine atom or an alkyl group at least one hydrogen atom is substituted with a fluorine atom. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group or a cycloalkyl group.
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group.
n represents an integer of 1 to 5.

8).
Resin (C) contains at least one acrylate or methacrylate repeating unit having any one of groups represented by general formulas (F2) to (F4) and general formulas (CS-1) to (CS-3) 8. The actinic ray-sensitive or radiation-sensitive resin composition as described in 7 above.
9.
The content of the resin (C) is 0.01 to 10% by mass with respect to the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition described.
10.
Furthermore,
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of 1 to 9 above, which comprises
11.
The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of 1 to 10 above, wherein the resin (A) contains a repeating unit containing a lactone structure.
12
The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of 1 to 11 above, wherein the resin (A) has a monocyclic or polycyclic acid-decomposable group.
13.
A resist film formed of the actinic ray-sensitive or radiation-sensitive resin composition according to any one of 1 to 12 above.
14
14. A pattern forming method comprising the steps of immersion exposure and development of the resist film described in 13 above.

  According to the present invention, the generation of line edge roughness and scum is improved, it is possible to form a pattern with less development defects, less acid elution into the immersion liquid, and good followability to the immersion liquid, Furthermore, there are provided an actinic ray-sensitive or radiation-sensitive resin composition excellent in various properties of particle suppression, pattern shape and bubble defect suppression, and a pattern forming method using the same.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what 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).
In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, electron beams and the like. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is represented not only by exposure to deep ultraviolet rays, X-rays, EUV light and the like, but also by particle beams such as electron beams and ion beams, unless otherwise specified, such as mercury lamps and excimer lasers. Drawing is also included in the exposure.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises (A) a resin whose solubility in an alkali developer increases by the action of an acid, which will be described later, and (C) at least two or more polar conversion groups. Containing a repeating unit having, and containing a resin having at least one of a fluorine atom and a silicon atom,
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
It is preferable to contain.

[1] Resin (A) whose solubility in an alkaline developer is increased by the action of an acid
The resin of component (A) is a resin whose solubility in an alkaline developer is increased by the action of an acid, and decomposes 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, It is a resin having a group that generates an alkali-soluble group (hereinafter also referred to as “acid-decomposable group”).
Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.
Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these alkali-soluble groups is substituted 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 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 to} 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 resin of component (A) preferably has a monocyclic or polycyclic acid-decomposable group. As the monocyclic or polycyclic acid-decomposable group, when any of R _{36 to} R ₃₉ is a cycloalkyl group, or R ₃₆ and R ₃₇ are connected to each other to form a ring. The structure is preferable.
The resin of component (A) preferably has a repeating unit having an acid-decomposable group. The repeating unit having an acid-decomposable group 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 hydroxyl group or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. An alkyl group, 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.
Examples of the alkyl group rx ₁ to Rx _3, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, those having 1 to 4 carbon atoms such as 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.
The cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. And a polycyclic cycloalkyl group such as an adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group is preferable.
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 polar group or a substituent containing a polar group, and when there are a plurality of them, each is independent. Specific examples of Z include the same as R ₁₀ in formula (2-1) described later. p represents 0 or a positive integer.

  The resin (A) is a resin having at least one of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) as the repeating unit represented by the general formula (AI). More preferably.

In formulas (1) and (2),
R ₁ and R ₃ each independently represent a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or 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 and may have a substituent.
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, more preferably 5 or 6.

R ₃ is preferably a hydrogen atom or a methyl group, and 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.
Specific examples and preferred examples of the organic group R ₉ is the same as those described for R ₉ in formula (AI).

Examples of the repeating unit represented by the general formula (1) include a repeating unit represented by the following general formula (1-1). In the formula, _{R 1} and _{R 2} have the same meanings as those in formula (1).

  The repeating unit represented by the general formula (2) is preferably a repeating unit represented by the following general formula (2-1).

In formula (2-1),
R < ₃ > -R < ₅ > is synonymous with the thing in General formula (2).
R ₁₀ represents a polar group or 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 polar group include a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, and the substituent containing the polar group is preferably a linear or branched alkyl group having these polar groups or A cycloalkyl group is mentioned, More preferably, it is an alkyl group which has a hydroxyl group. A branched alkyl group having a hydroxyl group is more preferable, and an isopropyl group is particularly preferable as the branched alkyl group.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

The resin (A) may contain a plurality of repeating units having an acid-decomposable group.
As described above, the resin (A) has at least one of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) as the repeating unit represented by the general formula (AI). It is more preferable that the resin contains. In another embodiment, the resin (A) is represented by at least two types of repeating units represented by the general formula (1) or the general formula (1) as the repeating units represented by the general formula (AI). It is more preferable that the resin contains both the repeating unit and the repeating unit represented by the general formula (2).
Moreover, while the resist composition of this invention contains multiple types of resin (A), the repeating unit which has an acid-decomposable group contained in these resin (A) may mutually differ. For example, you may use together resin (A) which has a repeating unit represented by General formula (1), and resin (A) which has a repeating unit represented by General formula (2).
As a preferable combination when the resin (A) contains a plurality of repeating units containing an acid-decomposable group and when the plurality of resins (A) have repeating units containing a different acid-decomposable group, for example, The following can be mentioned. In the following formula, each R independently represents a hydrogen atom or a methyl group.

  The resin of component (A) preferably further has a repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group.

The repeating unit having a lactone group that can be contained in the component (A) resin will be described.
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 selecting an optimal lactone group, the pattern profile, density dependency, line edge roughness, and development defects are improved.

The lactone structure portion 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 2 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. .

  Examples of the repeating unit having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-17) include a repeating unit represented by the following general formula (AII).

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group obtained by combining these. Preferably a single _bond, -Ab 1 -CO ₂ - is a divalent linking group represented by.
Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).

  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 repeating unit having a lactone group is preferably a repeating unit having a lactone structure represented by the following general formula (3).

In formula (3),
A represents an ester bond (—COO—) or an amide bond (—CONH—).
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof independently when there are a plurality of R ₀ .
Z is independently an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond when there are a plurality of Z.
R ₈ represents a monovalent organic group having a lactone structure.
n is the repeating number of the structure represented by -R < ₀ > -Z- in the repeating unit represented by Formula (3), and represents an integer of 1 to 5.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent.

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 -An alkoxy group such as butoxy group and benzyloxy group, and an acyloxy group such as acetyloxy group and propionyloxy group. 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. Preferred cycloalkylene is cycloalkylene having 4 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 specific examples are represented by the same general formulas (LC1-1) to (LC1-17) as described above. The lactone structure represented is mentioned, Of these, 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.

  The repeating unit having a lactone structure is more preferably a repeating unit represented by the following general formula (3-1).

In general formula (3-1),
R ₇ , A, R ₀ , Z, and n are as defined in the general formula (3).
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, and} 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, 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, an alkoxycarbonyl group, or a cyano 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.

Particularly preferred repeating units having a lactone group include the following repeating units.
In specific examples,
Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .
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 trifluoromethyl group or a hydroxymethyl group which is an alkyl group having a substituent, or Represents an acetyloxymethyl group.

As for the content rate of the repeating unit which has a lactone group, 15-60 mol% is preferable with respect to all the repeating units in resin, More preferably, it is 20-50 mol%, More preferably, it is 30-50 mol%.
Further, the resin (A) may contain one type of repeating unit having a lactone group or a plurality of types.
In order to enhance the effects of the present invention, two or more lactone repeating units selected from the general formula (3) can be used in combination. When using together, it is preferable to select and use 2 or more types from the lactone repeating unit in which n is 1 in general formula (3). Moreover, it is also preferable to use together the lactone repeating unit whose Ab is a single bond in General formula (AII), and the lactone repeating unit whose n is 1 among General formula (3).

In addition to the repeating unit represented by the above general formula (AI) and the repeating unit having a lactone group (when they have a hydroxyl group or a cyano group), the resin as the component (A) is a repeating unit having a hydroxyl group or a cyano group. It is preferable to have. 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. Preferred examples of the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group include a monohydroxyadamantyl group, a dihydroxyadamantyl group, a monohydroxydiamantyl group, a dihydroxydiamantyl group, and a norbornyl group substituted with a cyano group. It is done.
As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following 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 rest are hydrogen atoms. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms.

  Examples of the repeating unit having a partial structure represented by the 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 (A).

  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 of component (A) preferably has 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 bissulfonylimide 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 (A), 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. Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

  As the repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group and an alkali-soluble group, more preferably, a repeating unit having at least two groups selected from a lactone group, a hydroxyl group, a cyano group and an alkali-soluble group Preferably, it is a repeating unit having a cyano group and a lactone group. Particularly preferred is a repeating unit having a structure in which a cyano group is substituted on the lactone structure of (LCI-4).

  It is preferable that the resin of component (A) further contains a repeating unit represented by the general formula (I) that has neither a hydroxyl group nor a cyano group.

In general formula (I), 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 an alkyl group or an acyl group. Examples of Ra include H, CH ₃ , CF _{3 and the} like.

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 2 to 4 carbon atoms.

The content of the repeating unit represented by the general formula (I) having neither a hydroxyl group nor a cyano group is preferably from 0 to 40 mol%, more preferably based on all repeating units in the resin (A). 0 to 20 mol%.
Specific examples of the repeating unit represented by the general formula (I) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ or CF ₃ .

  In addition to the above repeating structural units, the resin of component (A) can be dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties of resist, such as resolution, heat resistance, and sensitivity. Various repeating structural units can be included for the purpose of adjusting the above.

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

  As a result, the performance required for the resin of component (A), in particular, (1) solubility in coating solvent, (2) film forming property (glass transition point), (3) alkali developability, (4) film slipping Fine adjustments such as (hydrophobicity and alkali-soluble group selection), (5) adhesion of the unexposed part to the substrate, and (6) dry etching resistance are possible.

  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 of component (A), the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist performance required for resolving power and heat resistance. In order to adjust the sensitivity and the like, it is set as appropriate.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure, the resin of component (A) has substantially no aromatic group from the viewpoint of transparency to ArF light. (Specifically, the ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, an aromatic group. The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
Further, the resin of the component (A) of the present invention is preferably a resin different from the resin (C), and preferably contains no fluorine atom or silicon atom from the viewpoint of compatibility with the resin (C). .

  As the resin of component (A), preferably, 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. More preferably, the (meth) acrylate repeating unit having an acid-decomposable group represented by the general formula (AI) is 20 to 50 mol%, the (meth) acrylate repeating unit having a lactone group is 20 to 50 mol%, It is a copolymer having 5 to 30 mol% of (meth) acrylate-based repeating units having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and further containing 0 to 20 mol% of other (meth) acrylate-based repeating units. .

  In the case where the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin as component (A) Preferably has a hydroxystyrene-based repeating unit in addition to the repeating unit represented by formula (AI). More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such as a (meth) acrylic acid tertiary alkyl ester.

  Preferred examples of the repeating unit having an acid-decomposable group include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, a repeating unit of (meth) acrylic acid tertiary alkyl ester, and the like. The repeating unit by 2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate is more preferable.

The resin of component (A) 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, 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, Further, the composition of the present invention such as propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), and cyclohexanone described later is used. Solvents that dissolve are mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. 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. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.
The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

The weight average molecular weight of the component (A) resin is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and still more preferably 3,000 as a polystyrene-converted value by the GPC method. ˜15,000, particularly preferably 5,000 to 13,000. 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 degree of dispersion (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 1.7. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the sidewall of the resist pattern, the better the roughness.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the mixing ratio of the component (A) resin in the entire composition is preferably 50 to 99% by mass, more preferably 70 to 98% in the total solid content. It is 70 mass%, More preferably, it is 70-95 mass%.
In the present invention, the resin of component (A) may be used alone or in combination (polymer blend).

[2] Compound (B) that generates an acid upon irradiation with an actinic ray or radiation
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a compound that generates an acid upon irradiation with an actinic ray or radiation (hereinafter also referred to as “acid generator”).
As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, or irradiation with actinic ray or radiation used for micro resist Known compounds that generate acids 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 compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 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. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Z ⁻ represents a non-nucleophilic anion.

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

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

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

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

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

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

  The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), 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 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), ant 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.

Examples of the non-nucleophilic anion of Z ⁻ include an aliphatic sulfonate anion in which the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group. A bis (alkylsulfonyl) imide anion substituted with a fluorine atom and a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compounds (ZI-1) to (ZI-4) described later.

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

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

The aryl group for R _{204 to} R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R _{204 to} R ₂₀₇ 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.

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

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ 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).

  More preferred (ZI) components include compounds (ZI-1) to (ZI-4) described below.

The compound (ZI-1) is an arylsulfonium compound in which at least one of R _{201 to} R _{203 in} the general formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest 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.

The aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ are 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 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 not containing an 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.

As the alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ , a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). 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 (eg, 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 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a hydroxyl group, or a nitro group. Or represents 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, a sulfur atom , An ester bond and an amide bond may be included.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.
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, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

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 aryl group as R _{1c to} R _5c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

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) ).
Specific examples of the alkoxy group in the alkoxycarbonyl group as R _1c to R _5c are the same as specific examples of the alkoxy group of _R 1c _{to R 5c.}
Specific examples of the alkyl group in the alkylcarbonyloxy group as R _1c to R _5c are the same as specific examples of the alkyl group of _R 1c _{to R 5c.}
Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R _1c to R _5c are the same as specific examples of the cycloalkyl group of _R 1c _{to R 5c.}
Specific examples of the aryl group in the aryloxy group as R _{1c to} R _{5c are the same} as the specific examples of the aryl group as R _{1c to} R _5c .

Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.
The ring structure that any two or more of R _{1c to} R _5c may be bonded to each other is preferably a 5-membered or 6-membered ring, particularly preferably a 6-membered ring (eg, a phenyl ring). It is done.

_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, and include 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 .

With respect to the alkoxy group in the alkoxycarbonylmethyl group, the same alkoxy groups as in R _{1c to} R _5c can be exemplified.

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 allyl group is not particularly limited, but may be an unsubstituted allyl group or an allyl group substituted with a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). Is preferred.
The vinyl group is not particularly limited, but is an unsubstituted vinyl group or a vinyl group substituted with a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). Is preferred.

  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 a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, or a cycloalkylsulfonyl group.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring.
l represents an integer of 0-2.
r represents an integer of 0 to 10.
Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n -An octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group etc. can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are preferable.
Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, norbornyl, tricyclo Examples include decanyl, tetracyclodecanyl, adamantyl and the like, and cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl are particularly preferable.
The alkoxy group of R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n -Butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group and the like can be mentioned. Of these alkoxy groups, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and the like are preferable.

The alkoxycarbonyl group for R ₁₃ is linear or branched and preferably has 2 to 11 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, or an i-propoxycarbonyl group. N-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyl Examples thereof include an oxycarbonyl group, an n-octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, an n-nonyloxycarbonyl group, and an n-decyloxycarbonyl group. 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 of R ₁₄ are linear, branched, or cyclic, and preferably those having 1 to 10 carbon atoms, such as methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl. Group, n-butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group, neopentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group n -Nonanesulfonyl group, n-decanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group, etc. can be mentioned. Of these alkylsulfonyl groups, 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. Examples thereof include an alkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group.
Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, Examples thereof include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as a cyclohexyloxy group.
Examples of the alkoxyalkyl group include straight chain having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group. Examples thereof include a chain, branched or cyclic alkoxyalkyl group.
Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t Examples thereof include linear, branched or cyclic alkoxycarbonyl groups having 2 to 21 carbon atoms such as butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl and the like.
Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, and cyclopentyloxy. Examples thereof include linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyl group and cyclohexyloxycarbonyl.

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 ring structure 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. There may be a plurality of substituents for the ring structure, and they may be bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring, aromatic or non-aromatic heterocyclic ring, or these A polycyclic fused ring formed by combining two or more of the above rings may be formed.

R ₁₅ is preferably a methyl group, an ethyl group, a naphthyl group, or a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom. The alkyl group, cycloalkyl group, alkoxy group, or alkoxycarbonyl group of R _13, the alkyl group, cycloalkyl group, alkoxy group, alkylsulfonyl group, and cycloalkylsulfonyl group of R ₁₄ may be substituted as described above. The substituent is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

  Preferable specific examples of the cation in the compound represented by the general formula (ZI-4) are shown below.

  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.
Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI-1). Things can be mentioned.
Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ , R _209, and R ₂₁₀ include specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₁ , R _202, and R ₂₀₃ in the general formula (ZI-2), respectively. The same thing as an example can be mentioned.
The alkylene group of A is alkylene having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 to 2 carbon atoms. 12 alkenylene groups (for example, ethynylene group, propenylene group, butenylene group, etc.), and the arylene group of A is an arylene group having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Can be mentioned.

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

  Specific examples of preferable cations generated from the acid generator include cations represented by the following formula.

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

  The compound that generates an acid is preferably a compound that generates an acid represented by the following general formula (1).

In the general formula (1), R _{1 to} R ₈ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a hydroxyl group. R ₉ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, —CORx, or —SO ₂ Rs. A represents a divalent linking group containing a hetero atom or a single bond. Rx represents an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group. Rs represents an alkyl group, a cycloalkyl group or an aryl group. m1 to m4 each independently represents an integer of 0 to 12. However, m3 + m4 ≧ 1. m5 represents an integer of 1 to 3. A plurality of R _{1 to} R ₈ or A that are plural when any one of m1 to m5 is 2 or more may be the same or different.
Here, the alkyl group, cycloalkyl group, and alkenyl group may have a fluorine atom as a substituent. Rs may further have one or more substituents. Examples of such substituents include an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms) and an alkoxy group (preferably May be a linear or branched alkoxy group having 1 to 4 carbon atoms.

Examples of the divalent linking group containing a hetero atom of A, an oxygen _{atom, -CO -, - CONR -,} - SO 2 NR -, - CONRCO -, - SO 2 NRCO -, - SO 2 NRSO 2 -, or - OCONR-. Here, R represents a hydrogen atom, an alkyl group, or a cycloalkyl group.
R _{1 to} R ₈ are each independently preferably a hydrogen atom, a perfluoroalkyl group, or a fluorine atom, and more preferably a perfluoroalkyl group or a fluorine atom. A is preferably a single bond or an oxygen atom. R ₉ is preferably an acyl group represented by —CORx. Rx is preferably a cycloalkyl group or an aryl group. In the general formula (1), the carbon atom adjacent to SO ₃ H is preferably substituted with a fluorine atom or a trifluoromethyl group.

  As a compound which generate | occur | produces the acid which has a structure represented by the said General formula (1), it is preferable that it is a structure represented by the following general formula (1-A).

In General Formula (1-A), R _{1 to} R ₉ , A, and m1 to m5 are respectively synonymous with R _{1 to} R ₉ , A, and m1 to m5 in General Formula (1), and M ⁺ Represents an organic counter cation.
The organic counter ion represented by M ⁺ is preferably an iodonium or sulfonium ion, particularly preferably a sulfonium ion.

Examples of the organic counter ion represented by M ⁺ include cations in the general formulas (ZI) and (ZII), cations represented by the general formula (IIId) described later, and the like.
The onium cation M ⁺ is more preferably a cation in the compound represented by the general formula (ZI-4).

  The acid represented by the general formula (1) is more preferably a structure represented by the following general formulas (1-B) to (1-D).

In General Formula (1-B) to (1-D), R ₉ has the same meaning as R ₉ in General Formula (1), and m6 represents an integer of 0 to 2.
As a compound which generate | occur | produces the acid represented by General formula (1), it is especially preferable that it is a structure represented by the following general formula (1-E)-(1-G).

In formula (1-E) ~ (1 -G), m6 is the same meaning as m6 in the general formula (1-D), _{R 9} and ^{M +} is and _{R 9} in the above formula (1-A) It is synonymous with M ⁺ .

Although the specific example of the photo-acid generator which generate | occur | produces the acid represented by General formula (1) below is shown, this invention is not limited to this. In the following specific examples, M ⁺ represents the organic counter cation.

  As the acid generator, a compound represented by the following general formula (I) is also preferable.

In general formula (I),
X ⁺ represents an organic counter ion, and R represents a hydrogen atom or an organic group.
R represents a hydrogen atom or an organic group, preferably an organic group having 1 to 40 carbon atoms, more preferably an organic group having 3 to 20 carbon atoms, and an organic group represented by the following formula (II). Most preferably it is a group.
The organic group for R may have one or more carbon atoms. Preferably, the atom bonded to the oxygen atom in the ester bond represented by the general formula (I) is a carbon atom, such as an alkyl group, Examples include a cycloalkyl group, an aryl group, an aralkyl group, and a group having a lactone structure, and the chain may have a hetero atom such as an oxygen atom or a sulfur atom. These may have each other as a substituent, and may have a substituent such as a hydroxyl group, an acyl group, an acyloxy group, an oxo group (═O), or a halogen atom.

_{- (CH 2) n -Rc- (} Y) m formula (II)
In formula (II),
Rc represents a monocyclic or polycyclic organic group (preferably having 3 to 30 carbon atoms) which may contain a cyclic ether, a cyclic thioether, a cyclic ketone, a cyclic carbonate, a lactone, or a lactam structure.
Y is a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a hydrocarbon group (preferably 1 to 10 carbon atoms), a hydroxyalkyl group (preferably 1 to 10 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms). ), An acyl group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably 2 to 10 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxyalkyl group (preferably 2 to 10 carbon atoms). ), A halogenated alkyl group (preferably having 1 to 8 carbon atoms).
m is an integer of 0 to 6, and when a plurality of Y are present, they may be the same as or different from each other.
n is an integer of 0-10.
The total number of carbon atoms constituting the organic group represented by formula (II) is preferably 40 or less.
n is 0 to 3, and Rc is preferably a monocyclic or polycyclic organic group having 7 to 16 carbon atoms.
The molecular weight of the compound represented by the general formula (I) is generally 300 to 1000, preferably 400 to 800, and more preferably 500 to 700.

Examples of the organic counter ion of X ⁺ include a sulfonium cation and an iodonium cation.
In the compound of the general formula (I), as a preferable embodiment, a compound represented by the general formula (Z _SC1 ) or the general formula (Z _IC1 ) can be given.

In the above general formula (Z _SC1 ),
The definition and preferred range of R are the same as the definition in general formula (I).
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
Specific examples of the organic group of R _{201, R 202} and _{R 203,} such as a preferred embodiment is the same as _{R 201, R 202} and _{R 203} in formula (ZI).
In general formula (Z _IC1 ),
The definition and preferred range of R are the same as the definition in general formula (I).
R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
Aryl group of R ₂₀₄ and _{R 205,} Examples and preferred embodiments of the alkyl group or cycloalkyl group, the general formula (ZII), an aryl group of _{R 204} and _{R 205} in (ZIII), an alkyl group or a cycloalkyl The same as described above.

In addition, the compound which has two or more structures represented by general formula ( _ZSC1 ) may be sufficient. For example, the general formula at least one of _R 201 _{to R 203} of a compound represented by _{(Z SC1),} bound to at least one of _R 201 _{to R 203} of another compound represented by the general formula _{(Z SC1)} It may be a compound having a structure.

  The compound represented by the general formula (I) can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.

  As an acid generator, the compound which generate | occur | produces the acid represented by general formula (IA) or (IB) by irradiation of actinic light or a radiation is also preferable.

In general formula (IA) and general formula (IB),
R _{1 to} R ₈ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a hydroxyl group. However, at least one of R _{1 to} R ₈ is a fluorine atom or a group having a fluorine atom.
A ₁ and A ₂ each independently represents a divalent linking group or a single bond.
R represents a substituent. When a plurality of Rs are present, two or more Rs may be bonded to each other to form a ring.
k represents an integer of 0 to 5. n represents an integer of 0 to 5. m1 to m4 each independently represents an integer of 0 to 12. However, at least one of m1 to m4 is 1 or more.

Examples of the divalent linking group for A ₁ and A ₂ include —O—, —S—, carbonyl group, ester group, sulfinyl group, sulfonyl group, methylene group, 1,1-ethylene group, 1,2- Ethylene group, propylene group, 1-methylpropylene group, 1-ethylpropylene group, trimethylene group, difluoromethylene group, tetrafluoro-1,2-ethylene group, 1,2-phenylene group, 1,3-phenylene group, 1 , 4-phenylene group, or a group formed by combining two or more of these. Of these divalent groups, a carbonyl group, an ester group, a methylene group, a difluoromethylene group, a tetrafluoro-1,2-ethylene group and the like are preferable.

Examples of the substituent for R include an oxo group (═O), a hydroxyl group, a carboxyl group, a formyl group, an alkyl group (straight or branched, preferably 1 to 10 carbon atoms), a vinylidene group (directly). Chain or branched, preferably 1 to 10 carbon atoms, monovalent cyclic organic group (preferably 3 to 12 carbon atoms), aryl group (preferably 6 to 20 carbon atoms), alkoxy group (straight or Branched, preferably 1 to 10 carbon atoms, aryloxy group (preferably 6 to 20 carbon atoms), alkylcarbonyl group (straight or branched, preferably 2 to 10 carbon atoms), arylcarbonyl group (preferably Has 7-20 carbon atoms), an alkoxycarbonyl group (straight or branched, preferably 2-10 carbon atoms), an aryloxycarbonyl group, etc. (preferably 7-2 carbon atoms). ) Can be mentioned.
As the substituent for R, an oxo group (═O), an alkyl group, an alkoxy group, an alkylcarbonyl group (straight or branched, preferably 2 to 10 carbon atoms), and an alkoxycarbonyl group are preferable.

Examples of the alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- An octyl group, n-nonyl group, n-decyl group, etc. can be mentioned.
Examples of the vinylidene group include a carbenyl group, a 1,1-ethylidenyl group, a propylidenyl group, a 1-methylpropylidenyl group, and a 1-ethylpropylidenyl group.
Examples of the monovalent cyclic organic group include a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a camphoroyl group.

Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a p-hydroxyphenyl group, a 1-naphthyl group, a 1-anthracenyl group, and a benzyl group.
As an alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group etc. can be mentioned, for example.
Examples of the aryloxy group include a phenoxy group, a p-hydroxyphenoxy group, an o-tolyloxy group, an m-tolyloxy group, and a p-tolyloxy group.

Examples of the alkylcarbonyl group include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, t-butylcarbonyl group and the like.
Examples of the arylcarbonyl group include a phenylcarbonyl group and a benzylcarbonyl group.
Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group and the like.

  Examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a benzyloxycarbonyl group. In addition, these substituents can also have arbitrary substituents, for example, 1 or more types of the above-mentioned substituents.

  R can be bonded to any of the carbon atoms constituting the norbornene ring or norbornane ring in each formula, and when there are a plurality of R, they may be the same or different from each other. When a plurality of Rs are present, two or more Rs may be bonded to each other to form a ring. That is, at least two or more Rs may be bonded to each other to form a ring together with the carbon atom to which they are bonded.

  k is preferably 0, and n is preferably 0 or 1.

  In the structure represented by the formula (IA) and the structure represented by the formula (IB), the structure represented by the formula (IA) is more preferable from the viewpoint of absorption intensity at a wavelength such as 193 nm. preferable.

  Preferable examples of the acid represented by general formula (IA) and general formula (IB) include, for example, the structures shown in the following formulas.

  The compound that generates an acid represented by general formula (IA) or (IB) is more preferably a structure represented by the following general formula (II-A) or (II-B).

In general formula (II-A) and general formula (II-B),
Z ₁ and Z ₂ each independently represents a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group.
Y ₁ represents a single bond or a divalent group.
R represents a substituent. When a plurality of Rs are present, two or more Rs may be bonded to each other to form a ring.
M ⁺ represents a monovalent onium cation.
k represents an integer of 0 to 5. n represents an integer of 0 to 5.

The perfluoroalkyl group of Z ₁ and Z ₂ may be linear or branched, and preferably has 1 to 10 carbon atoms.
The perfluorocycloalkyl group of Z ₁ and Z ₂ may be monocyclic or polycyclic, and is preferably a perfluorocyclohexyl group, a perfluorocyclopentyl group, or the like.

Examples of the divalent group for Y ₁ include the same groups as those for A ₁ and A ₂ in the general formulas (IA) and (IB). R, k, and n are the same as those in formulas (IA) and (IB).

The monovalent onium cation represented by M ⁺ is preferably an iodonium or sulfonium ion, more preferably a sulfonium ion, specifically, a cation or the like in the general formulas (ZI) and (ZII) More preferably, the cation in the said general formula (ZI) is mentioned.
Alternatively, a cation represented by the following general formula (IIId) is also preferable.

In formula (IIId):
P ₁₀ to P ₂₁ each independently represent hydrogen atom, a hydroxyl group, an alkyl group (preferably having 1 to 12 carbon atoms), a cycloalkyl group (preferably 3 to 12 carbon atoms), an alkoxy group (preferably 1 to carbon atoms 12) or a halogen atom (fluorine, chlorine, bromine, iodine).
Y represents a sulfur atom or an oxygen atom.
m represents 0 or 1.
Alkyl group of P ₁₀ to P _21, a cycloalkyl group, an alkoxy group include the same as those in _R 1c _{to R 5c} in the formula (ZI-3).
These groups may further have a substituent, and the substituent that may further have an organic group (preferably an organic group having 1 to 40 carbon atoms, more preferably 3 carbon atoms). -20 organic groups). Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a group having a lactone structure, and the chain may have a hetero atom such as an oxygen atom or a sulfur atom. .

Moreover, as a preferable form of the sulfonium ion as M ⁺ in the general formula (II-A) and the general formula (II-B), a sulfonium ion represented by the following general formula (IIIe) can be given.

_Wherein, P 22 _{to P 24} each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms).

Examples of the alkyl group for P _{22 to} P ₂₄ include the same as those for R _{1c to} R _5c in formula (ZI-3).
These groups may further have a substituent, and examples of the substituent that may be further included include the above specific examples of the substituent that each group in the general formula (IIId) may further have. The same thing is mentioned.

  Among acid generators, particularly preferred examples are given below.

  Although the compound shown below is mentioned as a compound which generate | occur | produces the sulfonic acid represented by general formula (IA) or (IB), It is not limited to these.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 30% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, 0.1-20 mass% is more preferable, More preferably, it is 0.5-15 mass%, Most preferably, it is 1-13 mass%.

  [3] Resin (C) containing a repeating unit having at least two polar conversion groups and having at least one of a fluorine atom and a silicon atom

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a repeating unit (c) having at least two or more polar conversion groups and has at least one of a fluorine atom and a silicon atom ( C). The resin (C) is hydrophobic, but the addition of the resin (C) is particularly preferable from the viewpoint of reducing development defects.
The fluorine atom may be a fluorine atom as an electron withdrawing group in a polarity conversion group described later, or may be a fluorine atom different from the fluorine atom as the electron withdrawing group.
The repeating unit (c) is preferably a repeating unit (c ′) having at least two or more polar conversion groups and at least one of a fluorine atom and a silicon atom on one side chain. That is, it is a repeating unit having a structure having at least one of a fluorine atom and a silicon atom on a side chain having a plurality of polarity converting groups.

Further, the repeating unit (c) is a repeating unit (c *) having at least two or more polar conversion groups and having no fluorine atom and silicon atom, and the resin (C) is a fluorine atom and silicon. It is also preferable to further have a repeating unit having at least one of atoms.
Alternatively, the repeating unit (c) has at least two or more polar conversion groups on one side chain, and a fluorine atom and a silicon atom on a side chain different from the side chain in the same repeating unit. It is also preferred that it is a repeating unit (c ″) having at least one. In this case, 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 the carbon atoms of the main chain. It is preferable that the α-position is in a positional relationship such as the following formula (4), wherein B1 is a partial structure having a polar conversion group, and B2 is at least one of a fluorine atom and a silicon atom. The partial structure which has.

  Of these embodiments of the resin (C), it is more preferable to have a repeating unit (c ′).

Here, the polar conversion group is a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer, and in the structure represented by the general formula (KA-1) or (KB-1). It is a partial structure represented by COO-.
The lactone structure represented by the general formula (KA-1) may be any group as long as it has a lactone ring, but is preferably a group having a 5- to 7-membered ring lactone structure, and 5 to 7-membered. Those in which other ring structures are condensed so as to form a bicyclo structure or a spiro structure in the ring lactone structure are preferred.

In addition, since the ester group (for example, -COO- in acrylate) directly bonded to the main chain of the resin in the repeating unit has a poor function as a polarity conversion group, it is not included in the polarity conversion group in this case.
Further, the repeating unit (c) may not have two separate entire structures represented by (KA-1) or (KB-1). It is understood that two attracting groups are included, whether in a form in which two ester structures are sandwiched or in a form of formula (KY-1) described later.
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).

In general formulas (KA-1) and (KB-1),
Z _ka 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, if Z _ka there are a plurality, the plurality of Z _ka same But it can be different.
Z _ka may be linked together to form a ring. Examples of the ring formed by linking Z _ka together include a cycloalkyl ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).
nka represents an integer of 0 to 10. Preferably it is an integer of 0 to 8, more preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.
X _kb1 and X _kb2 are each independently an electron withdrawing group.
nkb and nkb ′ each independently represents 0 or 1. When nkb and nkb ′ are 0, X _kb1 and X _kb2 are directly connected to an ester group (—COO—).
R _{kb1 to} R _kb4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group, and at least two of R _kb1 , R _kb2 and X _kb1 are connected to each other to form a ring _And at least two of R _kb3 , R _kb4 and X _kb2 may be connected to each other to form a ring.

The ring that may be formed by linking at least two of R _kb3 , R _kb4, and X _kb2 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 formulas (KA-1-1) to (KA-1-17) described later.

Note that the structure represented by the general formula (KA-1) or (KB-1) is the structure represented by the general formula (KA-1) ( _KB- ) when X _kb1 and X _kb2 are monovalent. When it does not have a bond as in the structure represented by 1), it is a monovalent or higher-valent partial structure obtained by removing at least one arbitrary hydrogen atom in the structure.

As an electron withdrawing group in Z _ka , X _kb1 , X _kb2 , R _{kb1 to} R _kb4 , a halogen atom, a cyano group, an oxy group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a nitrile group, a nitro group, a sulfonyl group A halo (cyclo) alkyl group or a haloaryl group represented by a group, a sulfinyl group, or —C (R _f1 ) (R _f2 ) —R _f3 , and combinations thereof.
The “halo (cyclo) alkyl group” represents an alkyl group or a cycloalkyl group that is at least partially halogenated. When the electron withdrawing group is a divalent or higher valent group, the remaining bond forms a bond with an arbitrary atom or substituent, and the main chain of the resin (C) through a further substituent It may be connected to.
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.
At least two of 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 an alkyl group in Z _ka and a structure in which this is halogenated.
In R _f1 to R _{f3, or,} as the (per) halocycloalkyl groups and (per) haloaryl groups in the ring and _{R f2} and _{R f3} is formed by connecting, halogenated cycloalkyl groups such as in the _{Z ka} And more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H and a perfluoroaryl 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.
More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.
The electron withdrawing group is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , more preferably —C ( CF _{3) 2} H or -C _{(CF 3)} a 2 CH _3.
In the electron withdrawing group, a part of fluorine atoms may be substituted with another electron withdrawing group.

Z _ka is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group or an electron withdrawing group, 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 _ka 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 _ka may have a substituent and may be linear or branched. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, for example, methyl group, ethyl group, n-propyl group, n-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, sec-butyl group, t-butyl group, i-pentyl group, Examples include t-pentyl group, 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 of Z _ka may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
The monocyclic cycloalkyl group preferably has 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.
Examples of the polycyclic cycloalkyl group include groups having a bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms. The polycyclic cycloalkyl group preferably has 6 to 20 carbon atoms. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group , Tetocyclododecyl group and androstanyl group.
Examples of these cycloalkyl groups include those represented by the following formula.

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, 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).

Examples of the Z _ka aryl group include a phenyl group and a naphthyl group.

Examples of the substituent that the alkyl group, cycloalkyl group, and aryl group of Z _ka may further include, for example, a hydroxyl group; a halogen atom; a nitro group; a cyano group; the above alkyl group; a methoxy group, an ethoxy group, a hydroxyethoxy group, Alkoxy groups such as 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, phenethyl group and cumyl group Aralkyloxy group; Aralkyloxy group; Acyl group such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group and valeryl group; Acyloxy group such as butyryloxy group; Alkenyl group; Vinyloxy group, propenyloxy group, allyloxy group And butenylo An alkenyloxy group such as a xy group; the above aryl group; an aryloxy group such as a phenoxy group; and an aryloxycarbonyl group such as a benzoyloxy group.

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.

As the lactone ring structure in the general formula (KA-1), a group having a lactone structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. Further, a group having a lactone structure may be directly bonded to the main chain. As a preferred lactone structure,
(KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1-14), (KA -1-17).
Specific examples of the skeleton having a lactone structure are shown below, but are not limited thereto.

  The lactone structure portion may or may not have a substituent. Preferred substituents include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, Examples include a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 4 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, and an acid-decomposable group. When a plurality of substituents are present, they may be the same or different, and the substituents may be bonded to form a ring.

  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, its optical purity (ee) is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more.

Since the structure represented by (KB-1) has a structure in which an electron withdrawing group is present at a position close to the ester structure, it has a high polarity conversion ability.
X _kb2 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by the above-mentioned —C (R _f1 ) (R _f2 ) —R _f3 .

  The at least two polarity conversion groups possessed by the repeating unit (c) are more preferably a partial structure having two polarity conversion groups represented by the following general formula (KY-1). Note that the structure represented by the general formula (KY-1) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In general formula (KY-1),
R _ky1 and R _ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and R _ky4 are bonded to the same oxygen atom to form a part of a carbonyl group (═O). May be formed.
R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. _{Examples of the} electron withdrawing group include the same groups as those of X _kb1 in the formula (KB-1), and are preferably a halogen atom or represented by -C (R _f1 ) (R _f2 ) -R _f3. A halo (cyclo) alkyl group or a haloaryl group.
At least two of R _ky1 , R _ky2 and R _ky4 may be linked to each other to form a monocyclic or polycyclic structure.
R _{kb1 to} R _kb4 , nkb, and nkb ′ are respectively synonymous with those in the formula (KB-1).

Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka in formula (KA-1).
As the lactone ring formed by linking R _ky1 and R _ky2 , the above (KA-1-1) to
The structure of (KA-1-17) is preferred. _{Examples of the} electron withdrawing group include the same groups as those in X _kb1 in the formula (KB-1).

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

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.
Two or more of R _{ky6 to} R _ky10 may be connected to each other to form a monocyclic or polycyclic structure.
R _ky5 represents an electron withdrawing group. _Examples of the electron withdrawing group include the same groups as those described above for X _kb1 in the formula (KB-1), and are preferably a halogen atom or represented by -C (R _f1 ) (R _f2 ) -R _f3. A halo (cyclo) alkyl group or a haloaryl group.
R _kb1 , R _kb2 and nkb have the same _meanings as those in formula (KB-1).
Specific examples of R _{ky5 to} R _ky10 include the same groups as Z _ka 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 _ka and nka each have the same meaning as in the general formula (KA-1). R _ky5 has the same _{meaning as} in formula (KY-2).
R _kb1 , R _kb2 and nkb have the same _meanings as those in formula (KB-1).
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.
Rs represents a chain or cyclic alkylene group, and when there are a plurality of Rs, they may be the same or different.
Ls represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Ls, they may be the same or different.
ns represents the number of repeating linking groups represented by-(Rs-Ls)-, and represents an integer of 0 to 5.

  The repeating unit (c) preferably has a structure represented by the formula (K0).

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 having a polarity converting group.
R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group having a polarity converting group. However, R _k1 and R _k2 as a whole have two or more polarity conversion groups.
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 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 Preferred are acrylate repeat units, vinyl ether repeat units, and norbornene repeat units, with acrylate repeat units being most preferred.

The resin (C) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a repeating unit having at least one of a fluorine atom and a silicon atom.
As a result, when the resin (C) is unevenly distributed on the surface layer of the actinic ray-sensitive or radiation-sensitive resin film and the immersion medium is water, the resist film surface with respect to water when the actinic ray-sensitive or radiation-sensitive resin film is used The receding contact angle can be improved, and the immersion water followability can be improved.
The receding contact angle of the actinic ray-sensitive or radiation-sensitive resin film is preferably 60 ° to 90 °, more preferably 65 ° or more, even more preferably at the temperature at the time of exposure, usually room temperature 23 ± 3 ° C. and humidity 45 ± 5%. Is 70 ° or more.
The content of the resin (C) in the actinic ray-sensitive or radiation-sensitive resin composition can be appropriately adjusted so that the receding contact angle of the actinic ray-sensitive or radiation-sensitive resin film falls within the above range, It is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. The resin (C) is ubiquitous at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and the polar / nonpolar substance is mixed uniformly. You don't have to contribute.
In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.
By having at least one of a fluorine atom and a silicon atom as the resin (C), the hydrophobicity (water followability) of the resist surface is improved, and the development residue (scum) is reduced.
The resin (C) is a resin having a plurality of polarity conversion groups and at least one of a fluorine atom and a silicon atom, and the fluorine atom is represented by X _kb1 , X in the general formula (KB-1) _{It may be} an electron withdrawing group of _kb2 .

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

The resin (C) is preferably a resin having a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group, or a fluorine atom-containing aryl group 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 are each independently a hydrogen atom, a fluorine atom, a linear or branched alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms), or an aryl group (preferably a carbon number). 6-14 aryl groups). _However, in each of _{R 57 ~R 61, R 62 ~R} 64 and _R 65 _{to R 68,} at least one, is a fluorine atom or at least one hydrogen atom is an alkyl group (preferably substituted with a fluorine atom the carbon number 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 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C
_{(C 2 F 5) 2 OH} , -C (CF 3) (CH 3) OH, -CH (CF 3) OH and the like, -C _{(CF 3)} 2 OH is preferred.

The resin (C) 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), but the present invention is limited to this. It is not a thing.

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, one or two selected from the group consisting of an alkylene group, a cycloalkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a ureylene group. A combination of the above groups can be mentioned.
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

  It is preferable that the groups represented by the general formulas (F2) to (F4) and the general formulas (CS-1) to (CS-3) are included in the acrylate or methacrylate repeating unit.

  Hereinafter, although the specific example of a repeating unit (c) is shown, this invention is not limited to this. Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

The content of the repeating unit (c) in the resin (C) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to the total repeating unit in the resin (C). 100 mol%, most preferably 40 to 100 mol%.
The content of the repeating unit (c ′) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, and most preferably 40, based on all repeating units in the resin (C). ˜100 mol%.
The content of the repeating unit (c *) is preferably from 10 to 90 mol%, more preferably from 15 to 85 mol%, still more preferably from 20 to 80 mol%, most preferably from 25 to the total repeating units in the resin (C). -75 mol%. The content of the repeating unit having at least one of a fluorine atom and a silicon atom used together with the repeating unit (c *) is preferably 10 to 90 mol%, more preferably based on all repeating units in the resin (C). It is 15 to 85 mol%, more preferably 20 to 80 mol%, and most preferably 25 to 75 mol%.
The content of the repeating unit (c ″) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, and most preferably 40 to the total repeating units in the resin (C). ˜100 mol%.

The resin (C) may further contain a repeating unit (c1) having at least one of a fluorine atom and a silicon atom and different from the repeating unit (c ′) · (c ″).
The fluorine atom or silicon atom in the repeating unit (c1) may be contained in the main chain of the resin or may be substituted with a side chain.

  Examples of the partial structure having a fluorine atom in the repeating unit (c1) include the same ones as described above, and may be directly bonded to a fluorine atom, and further 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 ureylene group may be used alone or in combination via a combination of two or more groups. The partial structure having a fluorine atom is preferably a group represented by the general formulas (F2) to (F4).

  Preferred examples of the repeating unit having a fluorine atom as the repeating unit (c1) include those shown below.

In the formula, R ₁₀ and R ₁₁ are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and particularly as an alkyl group having a substituent, Fluorinated alkyl group can be mentioned).
W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

  Besides these, resins having units as shown below are also applicable.

In the formula, R _{4 to} R ₇ are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and the alkyl group having a substituent is In particular, a fluorinated alkyl group can be mentioned). However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.
Q represents an alicyclic structure. The alicyclic structure may be monocyclic or polycyclic and may have a substituent. As the monocyclic type, a cycloalkyl group having 3 to 9 carbon atoms is preferable, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, norbornyl group, dicyclopentyl group. , Tricyclodecanyl group, tetocyclododecyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom. The alicyclic structure of Q is more preferably an alicyclic structure having 5 to 9 carbon atoms.
W ₂ represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).
L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or an alkyl group), —NHSO ₂ — or a divalent linking group obtained by combining a plurality of these.

Examples of the partial structure having a silicon atom in the repeating unit (c1) include the same ones as described above, and preferably include groups represented by the general formulas (CS-1) to (CS-3).
The repeating unit (c1) is preferably a (meth) acrylate repeating unit.

Hereinafter, although the specific example of a repeating unit (c1) is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ , and X ₂ represents —F or —CF ₃ .

The resin (C) may further have at least one group selected from the following groups (x) to (z).
(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) A group that decomposes by the action of an acid.

(X) Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.
Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

Examples of the repeating unit having an alkali-soluble group (x) include 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 main group of the resin via a linking group. Examples include a repeating unit in which an alkali-soluble group is bonded to the chain. Furthermore, 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. Is also preferable.
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 30 mol%, based on all repeating units in the resin (C). is there.

Specific examples of the repeating unit having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto. In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

In the resin (C), (y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer includes, for example, a group having a lactone structure, an acid anhydride group, and an acid imide group. And the like, preferably a group having a lactone structure.
The repeating unit having a group (y) that is decomposed by the action of an alkali developer and increases the solubility in an alkali developer includes the polarity converting group in the repeating unit (c) having at least two polar converting groups. A group having only one repeating unit is preferred, and a group that decomposes into the main chain of the resin by the action of an alkali developer and increases the solubility in the alkali developer, such as a repeating unit of an acrylate ester or methacrylate ester. Either a repeating unit to which (y) is bonded, or a polymerization initiator or chain transfer agent having a group (y) that increases the solubility in an alkali developer is introduced at the end of the polymer chain during polymerization. preferable.
The content of the repeating unit having a group (y) whose solubility in an alkali developer increases is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, based on all repeating units in the resin (C). More preferably, it is 5-20 mol%.

Specific examples of the repeating unit having a group (y) that increases the solubility in an alkali developer include the same repeating units as those having a lactone structure exemplified for the resin of the component (A).
Examples of the repeating unit having a group (z) that decomposes by the action of an acid in the resin (C) are the same as the repeating unit having an acid-decomposable group exemplified in the resin of the component (A). 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 is preferably a repeating unit represented by the following general formula (CAI).

In the general formula (CAI),
Xa ₁ represents a hydrogen atom, a methyl group or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl 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, 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.
Examples of the alkyl group rx ₁ to Rx _3, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, those having 1 to 4 carbon atoms such as 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.
The cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. And a polycyclic cycloalkyl group such as an adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
It is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group.
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.
In the resin (C), 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%, based on all repeating units in the resin (C). It is -80 mol%, More preferably, it is 20-60 mol%. (Z) LWR can be improved by having a group that decomposes by the action of an acid.

Resin (C) may further have other repeating units. Preferred examples of other repeating units include the following.
(Cy1) A repeating unit having a fluorine atom and / or a silicon atom, stable to an acid, and hardly soluble or insoluble in an alkali developer.
(Cy2) A repeating unit which does not have a fluorine atom or a silicon atom, is stable to an acid, and hardly soluble or insoluble in an alkali developer.
(Cy3) A repeating unit having a fluorine atom and / or a silicon atom and having a polar group other than the above (x) and (z).
(Cy4) A repeating unit having no fluorine atom or silicon atom and having a polar group other than the above (x) and (z).

In the repeating unit of (cy1) and (cy2), insoluble or insoluble in an alkali developer is a group in which (cy1) and (cy2) generate an alkali-soluble group or an alkali-soluble group by the action of an acid or an alkali developer. (For example, an acid-decomposable group or a polar converting group) is not contained.
The repeating units (cy1) and (cy2) preferably have an alicyclic hydrocarbon structure having no polar group.

The preferred embodiments of the repeating units (cy1) to (cy4) are shown below.
The repeating units (cy1) and (cy2) are preferably repeating units represented by the following general formula (CIII).

In general formula (CIII):
R _c31 represents a hydrogen atom, an alkyl group _optionally substituted with fluorine, a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a silicon atom, a fluorine atom, or the like.
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.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).
The repeating units (cy1) and (cy2) are preferably repeating units represented by the following general formula (C4) or (C5).

In the formula, R _c5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Rac represents a hydrogen atom, an alkyl group optionally substituted with fluorine, a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. Rac 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 _c5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms and a cycloalkenyl group having 3 to 12 carbon atoms. A preferable monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms.

  The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the bridged cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. The bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring (for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed). Preferred 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.

R _c6 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxycarbonyl group, or an alkylcarbonyloxy group. These groups may be substituted with a group containing a silicon atom, a fluorine atom, or the like.
The alkyl group for R _c6 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.
The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 20 carbon atoms.
n represents an integer of 0 to 5. When n is 2 or more, the plurality of R _c6 may be the same or different.
R _c6 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom, and particularly preferably a trifluoromethyl group or a t-butyl group.

  (Cy1) and (cy2) are preferably repeating units represented by the following general formula (CII-AB).

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

  The general formula (CII-AB) is more preferably the following general formula (CII-AB1) or general formula (CII-AB2).

In the formulas (CII-AB1) and (CII-AB2),
Rc ₁₃ ′ to Rc ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group.
In addition, at least two members out of Rc ₁₃ ′ to Rc ₁₆ ′ may combine to form a ring.
n represents 0 or 1.

Specific examples of (cy1) and (cy2) are listed below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

(Cy3) and (cy4) preferably have a repeating unit having a hydroxyl group or a cyano group as a polar group. This improves developer affinity. 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. 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 norbornyl group. Preferred examples of the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group include a monohydroxyadamantyl group, a dihydroxyadamantyl group, a monohydroxydiamantyl group, a dihydroxydiamantyl group, and a norbornyl group substituted with a cyano group. It is done.
Examples of the repeating unit having the atomic group include repeating units represented by the following general formulas (CAIIa) to (CAIId).

In the general formulas (CAIIa) to (CAIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms. In the general formula (CAIIa), more preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms.

  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 content of the repeating units represented by (cy1) to (cy4) is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 10%, based on all repeating units in the resin (C). 25 mol%. Resin (C) may have a plurality of repeating units represented by (cy1) to (cy4).

When resin (C) has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the molecular weight of the resin (C). Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% with respect to all the repeating units in resin (C), and it is more preferable that it is 30-100 mass%. When resin (C) has a silicon atom, it is preferable that the content rate of a silicon atom is 2-50 mass% with respect to the molecular weight of resin (C), and it is more preferable that it is 2-30 mass%.
Moreover, it is preferable that it is 10-90 mass% with respect to all the repeating units of resin (C), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-80 mass%.

  The weight average molecular weight of the resin (C) 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.

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

  As the resin (C), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, 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, Further, the composition of the present invention such as propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), and cyclohexanone described later is used. Solvents that dissolve are mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. The concentration of the reaction is usually 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).

  Although the specific example of resin (C) is shown below, this invention is not limited to this. The following table shows the molar ratio of repeating units in each resin (in order from the left in the structural formula), weight average molecular weight (Mw), and dispersity (Mw / Mn).

Resin (C) can be used individually by 1 type or in combination of 2 or more types.
Moreover, it is preferable to use it combining with resin (CP) which has at least any one of a fluorine atom or a silicon atom different from resin (C).

(CP) Resin having at least one of fluorine atom and silicon atom The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains at least one of fluorine atom and silicon atom separately from the resin (C). You may further contain resin (CP) which has. By containing the resin (C) / resin (CP), the resin (C) / resin (CP) is unevenly distributed in the surface layer of the film, and when the immersion medium is water, the resist film surface with respect to water when used as a film The receding contact angle can be improved, and the immersion water followability can be improved. The receding contact angle of the film is preferably 60 ° to 90 °, more preferably 70 ° or more. The content of the resin (CP) can be appropriately adjusted and used so that the receding contact angle of the film falls within the above range, but 0.01% based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is preferable that it is 10-10 mass%, More preferably, it is 0.1-5 mass%, More preferably, it is 0.1-4 mass%, Most preferably, it is 0.1-3 mass%. The resin (CP) is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and contributes to uniform mixing of polar / nonpolar substances. You don't have to.

In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. The contact angle of the immersion liquid with respect to the film in the film becomes important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.
By using the resin (C) and the resin (CP) in combination, the hydrophobicity (water followability) of the film surface is improved and the development residue (scum) is reduced.

The fluorine atom or silicon atom in the resin (CP) having at least one of a fluorine atom and a silicon atom may be present in the main chain of the resin or may be substituted with a side chain.
The resin (CP) 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 preferably include groups represented by the general formulas (F2) to (F4) in the resin (C). However, the present invention is not limited to this.
In this invention, it is preferable that group represented by general formula (F2)-(F4) is contained in a (meth) acrylate type repeating unit.

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 resin (CP) 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 general formulas (CS-1) to (CS-3) in the resin (C).

Furthermore, the resin (CP) may further have at least one group selected from the following groups (x) to (z).
(X) an alkali-soluble group, (y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer, and (z) a group that decomposes by the action of an acid.
Specific examples of these groups include the same groups as those in the resin (C).

The content of the repeating unit having a group (y) that increases the solubility in an alkali developer is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, based on all repeating units in the resin (CP). More preferably, it is 5-20 mol%.
Specific examples of the repeating unit having a group (y) that increases the solubility in an alkali developer include the same repeating units as those having a lactone structure exemplified for the resin of the component (A).

In the resin (CP), the repeating unit having a group (z) that is decomposed by the action of an acid may be the same as the repeating unit having an acid-decomposable group exemplified in the resin of the component (A). The content of the repeating unit having a group (z) that decomposes by the action of an acid in the resin (CP) is preferably from 1 to 80 mol%, more preferably 10%, based on all repeating units in the resin (CP). It is -80 mol%, More preferably, it is 20-60 mol%.
The resin (CP) may further have a repeating unit represented by the general formula (III) in the resin (C).

When resin (CP) has a fluorine atom, it is preferable that the content rate of a fluorine atom is 5-80 mass% with respect to the molecular weight of resin (CP), and it is more preferable that it is 10-80 mass%. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% with respect to all the repeating units in resin (CP), and it is more preferable that it is 30-100 mass%.
When resin (CP) has a silicon atom, it is preferable that the content rate of a silicon atom is 2-50 mass% with respect to the molecular weight of resin (CP), and it is more preferable that it is 2-30 mass%. Moreover, it is preferable that the repeating unit containing a silicon atom is 10-100 mass% with respect to all the repeating units of resin (CP), and it is more preferable that it is 20-100 mass%.
The weight average molecular weight of the resin (CP) 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.

  The resin (CP), like the resin of the component (A), is naturally low in impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably 0. -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 3, more preferably 1 to 2, and still more preferably, in terms of resolution, resist shape, resist pattern side walls, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

  As the resin (CP), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). Specifically, it can be synthesized in the same manner as the resin (C).

  Specific examples of the resin (CP) having at least one of a fluorine atom and a silicon atom are shown below.

[4] Solvent Examples of the solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl. Ether, alkyl lactate ester, alkoxypropionate alkyl, cyclic lactone (preferably 4 to 10 carbon atoms), monoketone compound (preferably 4 to 10 carbon atoms) which may contain a ring, alkylene carbonate, alkyl alkoxyacetate, pyrubin Examples thereof include organic solvents such as acid alkyls.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate. And propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene Preferred is 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 this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
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 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 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.

  The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate (PGMEA).

[5] Basic Compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound in order to reduce a 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 may be any of alkyl sulfonic acid ester, cycloalkyl group sulfonic acid ester, and aryl sulfonic acid ester. In the case of an alkyl sulfonate ester, the alkyl group has 1 to 20 carbon atoms, in the case of a cycloalkyl sulfonate ester, the cycloalkyl group has 3 to 20 carbon atoms, and in the case of an aryl sulfonate ester, the aryl group has 6 carbon atoms. ~ 12 are preferred. 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.

  The following compounds are also preferable as the basic compound.

  These basic compounds are used alone or in combination of two or more.

  The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of actinic-ray-sensitive or radiation-sensitive resin composition, Preferably it is 0.01-5 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. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

These basic compounds are the following ((D) low molecular compound having a group capable of leaving by the action of an acid (D) low molecular compound having a group capable of leaving by the action of an acid (D) / basic compound = 100). It is preferably used at a molar ratio (D) of low molecular compound / basic compound having a group capable of leaving by the action of the acid = 100/0 to 30/70, D) It is particularly preferable to use a low molecular compound / basic compound having a group capable of leaving by the action of an acid = 100/0 to 50/50.
In addition, the basic compound here does not include a low molecular compound having a group capable of leaving by the action of an acid (D) when it is also a basic compound.

[6] Low molecular weight compound (D) having a group capable of leaving by the action of an acid
The composition of the present invention may contain (D) a low molecular compound (also referred to as component D) having a group capable of leaving by the action of an acid. The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.
The molecular weight range of the low molecular weight compound having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.

  When the low molecular weight compound having a group capable of leaving by the action of an acid has a tertiary ester structure, it is particularly preferably a carboxylic acid ester or an unsaturated carboxylic acid ester represented by the following general formula (1a).

(In General Formula (1a), R ¹ independently represents a monovalent alicyclic hydrocarbon group (preferably having 4 to 20 carbon atoms) or a derivative thereof, or an alkyl group (preferably having 1 to 4 carbon atoms). And at least one of R ¹ is the alicyclic hydrocarbon group or a derivative thereof, or any two R ¹ are bonded to each other, and each of them is bonded to a carbon atom to which each is bonded. A cyclic hydrocarbon group (preferably having 4 to 20 carbon atoms) or a derivative thereof is formed, and the remaining R ¹ is an alkyl group (preferably having 1 to 4 carbon atoms) or a monovalent alicyclic hydrocarbon group ( Preferably, it has 4 to 20 carbon atoms or a derivative thereof.
X independently represents a hydrogen atom or a hydroxy group, and at least one is a hydroxy group.
A represents a single bond or a divalent linking group, preferably a single bond or a group represented by -D-COO-, and D represents an alkylene group (preferably having 1 to 4 carbon atoms). )

  In the general formula (1a), examples of the divalent linking group as A include a methylene group, a methylenecarbonyl group, a methylenecarbonyloxy group, an ethylene group, an ethylenecarbonyl group, an ethylenecarbonyloxy group, a propylene group, a propylenecarbonyl group, A propylene carbonyloxy group etc. are mentioned. Particularly preferred is a methylenecarbonyloxy group.

In the general formula (1a), a monovalent alicyclic hydrocarbon group of R ¹ (preferably having 4 to 20 carbon atoms) and a divalent alicyclic group formed by bonding any two R ¹ to each other. Examples of the hydrocarbon group (preferably having 4 to 20 carbon atoms) are derived from, for example, norbornane, tricyclodecane, tetracyclododecane, adamantane, cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. A group consisting of an alicyclic ring; a group consisting of these alicyclic rings is, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, 1 -The group etc. which were substituted by 1 or more types of C1-C4 alkyl groups and cycloalkyl groups, such as a methylpropyl group and t-butyl group, etc. are mentioned. Among these alicyclic hydrocarbon groups, a group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane, or a group consisting of these alicyclic rings is described above. A group substituted with an alkyl group is preferred.

  Examples of the alicyclic hydrocarbon group derivative include hydroxyl group; carboxyl group; oxo group (that is, ═O group); hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1- Hydroxypropyl groups having 1 to 4 carbon atoms such as hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group An alkoxyl group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group and a t-butoxy group; Group: C2-C5 such as cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc. A substituent such as Anoarukiru group can include one or more or one or more having groups. Of these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, a cyanomethyl group, and the like are preferable.

Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a t-butyl group. The C1-C4 alkyl group of these can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group are preferable.

  Preferable specific examples include the following compounds.

  When the low molecular weight compound is an unsaturated carboxylic acid ester, a (meth) acrylic acid ester is particularly preferable. Specific examples of the (meth) acrylic acid tertiary ester having a tertiary alkyl group as a group capable of leaving by the action of an acid are shown below, but are not limited thereto.

  As the low molecular compound (D) having a group capable of leaving by the action of an acid, a commercially available product or a compound synthesized by a known method may be used.

  Further, as the D component, an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

  The component D may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
R ′ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.
R ′ is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
The specific structure of the group represented by general formula (d-1) is shown below.

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

In General Formula (A), R _a independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When n = 2, two R _{a s} may be the same or different, and the two R _a are bonded to each other to form a heterocyclic hydrocarbon group (preferably having a carbon number of 20 or less) or a derivative thereof. It may be formed.
R _b independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
At least two R _b may be bonded to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

In the general formula (A), the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R _a and R _b are hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, etc. It may be substituted with a functional group, an alkoxy group, or a halogen atom.
R _a and R _b alkyl group, cycloalkyl group, aryl group or aralkyl group (these alkyl group, cycloalkyl group, aryl group and aralkyl group are substituted with the above functional group, alkoxy group or halogen atom). As well)
For example, a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., a group derived from these alkanes, for example, A group substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group,
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, groups derived from these cycloalkanes, for example, methyl group, ethyl group, n-propyl group, a group substituted with one or more linear or branched alkyl groups such as i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like,
Groups derived from aromatic compounds such as benzene, naphthalene, anthracene, etc., and groups derived from these aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 A group substituted with one or more linear or branched alkyl groups such as -methylpropyl group, 1-methylpropyl group, t-butyl group, and the like;
Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole, benzimidazole, groups derived from these heterocyclic compounds are linear or branched A group substituted with one or more groups derived from an alkyl group or aromatic compound, a group derived from a linear or branched alkane, a group derived from a cycloalkane, a phenyl group, a naphthyl group , A group substituted with one or more groups derived from an aromatic compound such as anthracenyl group or the like, or the above substituent is a hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo And a group substituted with a functional group such as a group.

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

Specifically shown in the present invention are particularly preferred examples: Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, ( S)-(−)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl- 4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxy Rubo sulfonyl morpholine, N-t-butoxycarbonyl piperazine, N, N-di -t- butoxycarbonylamino-1-adamantyl amine, N, N-
Di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonylhexamethylenediamine, N, N′-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8- Diaminooctane, N, N′-di-t-butoxycarbonyl-1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxy Carbonyl-1,12-diaminododecane, N, N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonyl Lens imidazole, N-t-butoxycarbonyl-2-methylbenzimidazole, N-t-butoxycarbonyl-2-phenylbenzimidazole, and the like.

  Although the especially preferable D component in this invention is shown concretely, this invention is not limited to this.

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

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

  In the present invention, the amount of the low molecular compound (D) having a group capable of leaving by the action of an acid is usually 0.001 to 20 mass based on the total solid content of the composition combined with the following basic compound. %, Preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

  The proportion of the low molecular compound having a group capable of leaving by the action of an acid generator and an acid in the composition is: acid generator / [low molecular compound having a group capable of leaving by the action of an acid (D) + the base Preferred compound] (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / [low molecular compound (D) having a group capable of leaving by the action of an acid + the basic compound] (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150. It is.

[7] Surfactant The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a surfactant, and when it is contained, a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant). It is preferable to contain any one of surfactants, silicon-based surfactants, surfactants having both fluorine atoms and silicon atoms, or two or more thereof.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains the above-mentioned surfactant, 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. It is possible to provide a resist pattern with less.
On the other hand, by making the addition amount of the surfactant small, for example, 10 ppm or less, the surface uneven distribution of the component (C) is improved, and thereby the resist film surface can be made more hydrophobic, and at the time of immersion exposure. The water following ability can be improved.
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 & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (Manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toagosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M , EF135M, EF351, EF352, EF801, E 802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (manufactured by Neos) Fluorine-based surfactants or silicon-based surfactants such as 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, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called 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, based on the total solid content (total amount excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. %, Particularly preferably 0.0005 to 1% by mass.

[8] Carboxylic acid onium salt The actinic ray-sensitive or radiation-sensitive resin composition in 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 having a molecular weight of 3000 or less, which decomposes by the action of an acid and increases the solubility in an alkaline developer. In addition, a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter, also referred to as “dissolution inhibiting compound”) that increases the solubility in an alkaline developer may be contained. 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 Processed of SPIE, 2724, 355 (1996), in order not to 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 (A) resin.

  When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, it contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. Those are preferred. 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 2 to 50% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 5% by mass with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. 10% by mass.

  Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

[10] Other additives The actinic ray-sensitive or radiation-sensitive resin composition of the present invention further has solubility in dyes, plasticizers, photosensitizers, light absorbers, and developers as necessary. A compound to be promoted (for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) and the like can be contained.

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 present invention also relates to a resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention.
Further, the pattern forming method of the present invention is characterized by including a step of immersion exposure and development of the resist film.
The actinic ray-sensitive or radiation-sensitive resin 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. preferable. 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 1.0 to 10% by mass, more preferably 1.0 to 8.0% by mass, and still more preferably 1.0. -6.0 mass%.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is prepared by dissolving the above-described components in a predetermined organic solvent, preferably the mixed solvent, filtered, and applied onto a predetermined support as follows. And use. 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 resist film.
The resist 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, and EUV (13 nm) are preferable.
In the present invention, electromagnetic waves such as ultraviolet light and X-rays are included in the radiation.

Before forming the resist film, an antireflection film may be coated on the substrate in advance.
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 are also used. it can.

In the development step, an alkaline developer is used as follows. Examples of the alkali developer for the positive resist composition include inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Alkaline aqueous solutions of cyclic amines such as quaternary ammonium salts such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
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.

  Exposure (immersion exposure) may be performed by filling a liquid (immersion medium) having a higher refractive index than air between the resist film and the lens during irradiation with actinic rays or radiation. Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.

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

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

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

In order to prevent the resist film from directly contacting the immersion liquid between the resist film and the immersion liquid of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, an immersion liquid hardly soluble film (hereinafter, (Also referred to as “top coat”). The functions necessary for the top coat are suitability for application to the upper layer of the resist, transparency of actinic rays or radiation (especially for 193 nm), and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the upper layer of the resist.
From the viewpoint of 193 nm transparency, the top coat is preferably a polymer that does not contain abundant aromatics. Specifically, the polymer contains a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, and silicon. Examples thereof include a polymer and a fluorine-containing polymer. The above-mentioned hydrophobic resin (C) is also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having a small penetration into the resist film is preferable. It is preferable that the peeling process can be performed with an alkali developer in that the peeling process can be performed simultaneously with the resist film development process. From the viewpoint of peeling with an alkaline developer, the topcoat is preferably acidic, but may be neutral or alkaline from the viewpoint of non-intermixability with the resist 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 top coat is preferably not mixed with the resist film and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the positive resist composition. 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 still in detail, the content of this invention is not limited by this.

Monomer Synthesis Example 1 (Synthesis of Compound (4))
The following compound (1) was synthesized by the method described in International Publication No. 07/037213 pamphlet.
150.00 g of water was added to 35.00 g of compound (1), and 27.30 g of NaOH was further added. The mixture was stirred for 9 hours under heating and reflux conditions. Hydrochloric acid was added to make it acidic, and the mixture was extracted with ethyl acetate. The organic layers were combined and concentrated to obtain 36.90 g of Compound (2) (yield 93%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.56-1.59 (1H), 1.68-1.72 (1H), 2.13-2.15 (1H), 2.13-2.47 (2H), 3.49-3.51 (1H), 3.68 (1H), 4.45-4.46 (1H)
200 ml of CHCl ₃ was added to 20.00 g of compound (2), and 50.90 g of 1,1,1,3,3,3-hexafluoroisopropyl alcohol and 30.00 g of 4-dimethylaminopyridine were further added and stirred. To the solution, 22.00 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred for 3 hours. The reaction solution was added to 500 ml of 1N HCl to stop the reaction. The organic layer was further washed with 1N HCl, then with water, and the organic layer was concentrated to obtain 30.00 g of Compound (3) (yield 85%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.62 (1H), 1.91-1.95 (1H), 2.21-2.24 (1H), 2.45-2.53 (2H), 3.61-3.63 (1H), 3.76 (1H), 4.32-4.58 (1H), 6.46-6.53 (1H)
While adding 300.00 g of toluene to 15.00 g of compound (3), further adding 3.70 g of methacrylic acid and 4.20 g of p-toluenesulfonic acid monohydrate, and removing the produced water by azeotropic distillation, 15 hours Refluxed. The reaction solution was concentrated, and the concentrate was purified by column chromatography to obtain 11.70 g of Compound (4) (yield 65%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.76-1.79 (1H), 1.93 (3H), 2.16-2.22 (2H), 2.57-2.61 (1H), 2.76-2.81 (1H), 3.73-3.74 (1H), 4.73 (1H), 4.84-4.86 (1H) , 5.69-5.70 (1H), 6.12 (1H), 6.50-6.56 (1H)

Monomer Synthesis Example 2 (Synthesis of Compound (8))
37.0 g of THF was added to 17.09 g of methyl glycolate (5) (manufactured by TCI), 21.15 g of triethylamine was further added, and the mixture was cooled to 0 ° C., and 20.85 g of methacrylic acid chloride was added dropwise. After returning to room temperature, the mixture was stirred for 2 hours. After adding an aqueous sodium hydrogen carbonate solution, the mixture was extracted with ethyl acetate. The organic layer was collected, MgSO ₄ was added, filtered and concentrated to obtain 28.51 g of compound (6) (yield 95%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.94-2.04 (3H), 3.71-3.72 (3H), 4.73 (2H), 5.72 (1H), 6.15 (1H)
180 ml of acetone was added to 28.5 g of compound (6), cooled to 0 ° C., and 180 ml of 1N NaOH water was added dropwise. After stirring for 30 minutes, the mixture was acidified with hydrochloric acid and extracted with ethyl acetate. The organic layer was collected, MgSO ₄ was added, filtered and concentrated to obtain 21.2 g of Compound (7) (yield 82%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.94-1.97 (3H), 4.71-4.72 (2H), 5.70-5.71 (1H), 6.15 (1H)
300 g of toluene was added to 15.00 g of compound (7), 7.00 g of compound (3) and 3.80 g of p-toluenesulfonic acid monohydrate were added, and the generated water was removed by azeotropic distillation for 6 hours. Refluxed. The reaction solution was concentrated, and the concentrate was purified by column chromatography to obtain 13.52 g of Compound (8) (yield 71%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.77-1.78 (1H), 1.95-1.96 (3H), 2.11-2.20 (2H), 2.56-2.61 (1H), 2.73-2.74 (1H), 3.73-3.75 (1H), 4.77-4.82 (4H), 5. 74 (1H), 6.16 (1H), 6.52-6.53 (1H)

Monomer Synthesis Example 3 (Synthesis of Compound (9))
Similar to Monomer Synthesis Example 1 except that 2,2,3,3,4,4,4-heptafluoro-1-butanol was used instead of 1,1,1,3,3,3-hexafluoroisopropyl alcohol In this manner, compound (9) was synthesized (3 step yield: 30%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.73-1.76 (1H), 1.93 (3H), 2.13-2.17 (1H), 2.57-2.61 (1H), 2.71-2.72 (1H), 2.77-2.81 (1H), 3.65-3.67 (1H), 4.69 (1H) , 4.79-4.80 (1H), 4.91-5.00 (2H), 5.68-5.69 (1H), 6.11-6.12 (1H)

Monomer Synthesis Example 4 (Synthesis of Compound (10))
Compound (10) was prepared in the same manner as in Monomer Synthesis Example 1 except that 1H, 1H-tridecafluoro-1-heptanol was used instead of 1,1,1,3,3,3-hexafluoroisopropyl alcohol. Synthesized (3 step yield 42%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.73-1.88 (1H), 1.93 (3H), 2.08-2.17 (1H), 2.56-2.61 (1H), 2.71-2.72 (1H), 2.77-2.81 (1H), 3.66-3.68 (1H), 4.69 (1H) , 4.79-4.81 (1H), 4.93-5.01 (2H), 5.68-5.69 (1H), 6.11-6.12 (1H)

Monomer Synthesis Example 5 (Synthesis of Compound (11))
Similar to Monomer Synthesis Example 1 except that 2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenol was used in place of 1,1,1,3,3,3-hexafluoroisopropyl alcohol. The compound (11) was synthesized by this method (3 step yield: 23%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.88-1.91 (1H), 1.94 (3H), 2.10-2.28 (2H), 2.66-2.71 (1H), 2.80 (1H), 3.92-3.93 (1H), 4.77 (1H), 4.90-4.92 (1H), 5.70 -5.71 (1H), 6.13-6.14 (1H)

Synthesis Example 1 Synthesis of Resin (C-8) Under a nitrogen atmosphere, 6.4 g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a three-necked flask and heated to 80 ° C. A solution in which 17.5 g of compound (1), 4.0 g of compound (2) and polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 58.0 g of PGMEA with respect to the monomer was added for 4 hours. It was hung and dropped. After completion of dropping, the reaction was further carried out at 80 ° C. for 4 hours. The reaction solution was allowed to cool and then added dropwise over a period of 20 minutes to a mixture of methanol 1300 g / distilled water 150 g. The precipitated powder was collected by filtration and dried, yielding 15.2 g of polymer (C-8).
The weight average molecular weight of the obtained polymer (C-8) was 8000 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.3.

  In the same manner, another resin (C) shown in the above table was synthesized.

Synthesis Example 2 Synthesis of Resin (1) Under a nitrogen stream, 8.6 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. To this, 9.8 g of 2-adamantyl isopropyl methacrylate, 4.4 g of dihydroxyadamantyl methacrylate, 8.9 g of norbornane lactone methacrylate, and 8 mol% of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries) were dissolved in 79 g of cyclohexanone. The 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 hexane 800 ml / ethyl acetate 200 ml over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 19 g of Resin (1). The weight average molecular weight of the obtained resin was 8800 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.9.
Similarly, another resin (A) shown below was synthesized.

  The structure of the acid-decomposable resin (A) used in the examples is shown below. The following table shows the molar ratio of repeating units in each resin (in order from the left in the structural formula), weight average molecular weight (Mw), and dispersity (Mw / Mn).

<Resist preparation>
The components shown in the following table were dissolved in a solvent to prepare a solution having a solid content concentration of 5% by mass, and this was filtered through a polyethylene filter having a pore size of 0.1 μm to prepare a positive resist composition. The prepared positive resist composition was evaluated by the following method, and the results are shown in the table. In the table, “resin (2 g)” means resin (A).

<Image performance test>
[Exposure conditions: ArF immersion exposure]
An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied on a 12-inch diameter silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. The positive resist composition prepared thereon was applied and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. The obtained wafer was exposed through a 6% halftone mask of 1: 1 line and space pattern with a line width of 75 nm using an ArF excimer laser immersion scanner (XT1250i, NA0.85, manufactured by ASML). Ultra pure water was used as the immersion liquid. Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.

[Line edge roughness (LER)]
For a range of 5 μm in the longitudinal direction of a 1: 1 line and space pattern with a line width of 75 nm, measure the distance from the reference line where there should be an edge by 50 points using a length measurement SEM (S-8840, manufactured by Hitachi, Ltd.). The standard deviation was obtained and 3σ was calculated. A value (nm) of less than 5.0 was rated as ◯, a value of 5.0 or more and less than 7.0 as Δ, and a value of 7.0 or more as x. A smaller value indicates better performance.

[Scum]
The development residue (scum) in a resist pattern having a line width of 75 nm was observed using a scanning electron microscope (S-4800, manufactured by Hitachi). The middle was marked with ◯ and △.

[Development defect evaluation]
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 (1 cm ² ) was calculated. A value of less than 0.5 was rated as ◎, a value of 0.5 or more and less than 0.7 as ◯, a value of 0.7 or more and less than 1.0 as Δ, and a value of 1.0 or more as x. A smaller value indicates better performance.

[Bubble defect]
An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied on a 12 inch silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. The positive resist composition prepared thereon was applied and heated and dried on a hot plate at 120 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.
The obtained wafer was exposed through a 6% halftone mask of 1: 1 line and space pattern with a line width of 75 nm using an ArF excimer laser immersion scanner (XT1250i, NA0.85, manufactured by ASML).
Ultra pure water was used as the immersion liquid. Thereafter, it was heated on a hot plate at 110 ° C. for 60 seconds.
Further, the resist film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 40 seconds, and then dried to obtain a resist pattern.
The number of development defects of the sample wafer thus obtained was measured with a KLA 2360 machine (manufactured by KLA Tencor).
The detected development defect site was observed using Hitachi measurement SEM: S9380, and the number of bubble defects was determined.
At this time, the number of bubble defects is 0 / cm ² , ◯, 0 / cm ² to 0.01 / cm ² or less, ○, 0.01 / cm ² to 0.1 Pieces / cm ² or less were evaluated as Δ, and those more than 0.1 pieces / cm ² as x.

[Pattern shape]
Observe an isolated pattern of 85 nm formed in the same manner as the bubble defect evaluation, ◎ for a rectangular shape, ○ for a substantially rectangular shape, △ for a slightly tapered shape, and × for a film loss. did.

<Other performance tests>
[Generated acid elution amount]
The prepared positive resist composition was applied on a silicon wafer having an 8 inch diameter and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 160 nm. Subsequently, the entire surface of the 8-inch wafer was exposed at 30 mJ / cm ² using an ArF excimer laser exposure machine (manufactured by ASML, PAS5500 / 1100). The wafer was immersed in a quartz container to which 100 mL of pure water deionized using an ultrapure water production apparatus (Nippon Millipore, Milli-Q) was added, and the eluate collected in water was collected. The amount of acid eluted into this aqueous solution was quantified by LC-MS.
LC device: 2695 manufactured by Waters
MS device: esquire 3000 manufactured by Brucker Daltonics
The detection intensity of ion species having a mass of 299 (corresponding to nonaflate anion) was measured with the LC-MS apparatus, and the elution amount of nonafluorobutanesulfonic acid was calculated. Similarly, the amount of elution was calculated for other anions. Elution amount is 1.0 × 10 ⁻¹⁰ mol / cm ² / sec or more x, smaller than 1.0 × 10 ⁻¹⁰ mol / cm ² / sec and 1.0 × 10 ⁻¹² mol / cm ² / sec or more. ( ^Triangle | delta) and less than 1.0 * 10 < ^-12 > mol / cm < ² > / sec were set as (circle).

[Backward contact angle]
The prepared positive resist composition was applied on a silicon wafer having an 8 inch diameter and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 160 nm. The receding contact angle of water droplets was measured by an expansion / contraction method using a dynamic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) at a room temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%. An initial droplet size of 35 μL was sucked at a speed of 6 μL / sec for 5 seconds, and a value with a stable dynamic contact angle during suction was defined as a receding contact angle. The larger the value of the receding contact angle, the more water can follow the higher scanning speed.

[Particle (Stability over time)]
About the prepared positive resist solution, the number of particles in the solution immediately after preparation (particle initial value) and the number of particles in the solution after standing for 1 week at 4 ° C. The particle increase number calculated by (number of particles after time) − (initial particle value) was calculated. Here, particles having a particle diameter of 0.25 μm or more contained in 1 mL of the solution were counted. )
Particles whose number of increase is 0.2 / ml or less are ◎, more than 0.2 / ml is 1 / ml or less ○, more than 1 / ml is 5 / ml or less △, more than 5 pieces / ml are taken as x.

The symbols in the table are as follows.
The acid generator and the resin (C) correspond to those exemplified above or the following.

[Basic compounds]
N-1: N, N-dibutylaniline N-2: N, N-dihexylaniline N-3: 2,6-diisopropylaniline N-4: tri-n-octylamine N-5: N, N-dihydroxyethyl Aniline N-6: 2,4,5-triphenylimidazole N-7: 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine N-8: 2,4,6-tri-t-butylaniline N-9: Nt-amyloxycarbonyl-4-hydroxypiperidine

[Surfactant]
W-1: Megafac F176 (Dainippon Ink Chemical Co., Ltd., fluorine-based)
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.)
W-5: PF656 (manufactured by OMNOVA, fluorine-based)
W-6: PF6320 (manufactured by OMNOVA, fluorine-based)

〔solvent〕
SL-1: Cyclohexanone SL-2: Propylene glycol monomethyl ether acetate (PGMEA)
SL-3: Ethyl lactate SL-4: Propylene glycol monomethyl ether (PGME)
SL-5: γ-butyrolactone SL-6: Propylene carbonate

  From Table 3, the resist pattern formed using the positive resist composition of the present invention has line edge roughness, scum, development defect, acid elution amount, followability to immersion liquid during immersion exposure, particles, pattern It was found that both the shape and bubble defects had excellent performance.

Claims (14)

A resin (A) whose solubility in an alkaline developer is increased by the action of an acid, and
Containing a repeating unit (c) having at least two polar conversion groups represented by —COO— in the structure represented by the general formula (KA-1) or (KB-1), and containing a fluorine atom and silicon An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (C) having at least one of atoms.

In general formulas (KA-1) and (KB-1),
Z _ka 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, if Z _ka there are a plurality, the plurality of Z _ka same But it can be different.
Z _ka may be linked together to form a ring.
nka represents an integer of 0 to 10.
X _kb1 and X _kb2 each independently represent an electron withdrawing group.
nkb and nkb ′ each independently represents 0 or 1.
R _{kb1 to} R _kb4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group, and at least two of R _kb1 , R _kb2 and X _kb1 are connected to each other to form a ring _And at least two of R _kb3 , R _kb4 and X _kb2 may be connected to each other to form a ring.   The repeating unit (c) is a repeating unit (c ′) having at least two or more polar conversion groups and at least one of a fluorine atom and a silicon atom on one side chain. Item 2. The actinic ray-sensitive or radiation-sensitive resin composition according to Item 1.   The repeating unit (c) is a repeating unit (c *) having at least two or more polar conversion groups and not having a fluorine atom and a silicon atom, and the resin (C) is further a fluorine atom and a silicon atom. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, comprising a repeating unit having at least one of the following.   The repeating unit (c) has at least two or more polar conversion groups on one side chain, and at least any one of a fluorine atom and a silicon atom on a side chain different from the side chain in the same repeating unit. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the composition is a repeating unit (c ″). The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (c) has a structure represented by the following general formula (KY-1).

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. R _ky1 and R _ky4 may be bonded to the same atom to form a double bond.
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.
At least two of R _ky1 , R _ky2 and R _ky4 may be linked to each other to form a monocyclic or polycyclic structure.
R _{kb1 to} R _kb4 , nkb, and nkb ′ are respectively synonymous with those in the formula (KB-1). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the repeating unit (c) has a structure represented by the following general formula (KY-2).

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.
R _kb1 , R _kb2 and nkb have the same _meanings as those in formula (KB-1). The resin (C) has at least one of groups represented by general formulas (F2) to (F4) and general formulas (CS-1) to (CS-3). 6. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of 6 above.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, a linear or branched alkyl group, or an aryl group. _However, in each of _{R 57 ~R 61, R 62 ~R} 64 and _R 65 _{to R 68,} at least one represents a fluorine atom or an alkyl group at least one hydrogen atom is substituted with a fluorine atom. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group or a cycloalkyl group.
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group.
n represents an integer of 1 to 5.   Resin (C) contains at least one acrylate or methacrylate repeating unit having any one of groups represented by general formulas (F2) to (F4) and general formulas (CS-1) to (CS-3) The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7.   Content of resin (C) is 0.01-10 mass% with respect to the total solid in actinic-ray-sensitive or radiation-sensitive resin composition, Any one of Claims 1-8 characterized by the above-mentioned. The actinic ray-sensitive or radiation-sensitive resin composition described in 1. Furthermore,
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, comprising:   Resin (A) contains the repeating unit containing a lactone structure, The actinic-light sensitive or radiation sensitive resin composition in any one of Claims 1-10 characterized by the above-mentioned.   Resin (A) has a monocyclic or polycyclic acid-decomposable group, The actinic-ray-sensitive or radiation-sensitive resin composition in any one of Claims 1-11 characterized by the above-mentioned.   A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1.   A pattern forming method comprising the steps of immersion exposure and development of the resist film according to claim 13.