JP5422447B2 - Actinic ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the same - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, and is used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film and a pattern forming method using the composition. In particular, the actinic ray-sensitive or radiation-sensitive resin composition suitable for exposure with an immersion type projection exposure apparatus using far-ultraviolet light having a wavelength of 300 nm or less as a light source, and a resist film and a pattern using the composition The present invention relates to a forming method.

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.
When exposure is performed using a scanning immersion exposure machine in the immersion exposure process, the exposure speed decreases unless the immersion liquid moves following the movement of the lens, which affects productivity. Is concerned. In the case where the immersion liquid is water, it is desirable that the resist film be hydrophobic because the water followability is good.

On the other hand, when the resist film is made hydrophobic, there is a problem that development defects adhering to the substrate or pattern after development increase.
Therefore, as a means of achieving both the above-described immersion exposure suitability and development defects, a polymer having a phenolate-based active ester group that can change the contact angle of the resist film surface with water by treatment with a base (alkaline developer) was added. A resist is disclosed in Patent Document 1.
Patent Documents 2 and 3 each disclose a resist to which a polymer compound having a specific protective group is added in order to obtain a resist material capable of forming a contact hole pattern with excellent roundness.
However, even if the compounds described in Patent Documents 1 to 3 above are added to impart immersion exposure suitability, development defects on the pattern are not sufficiently reduced, particularly in the formation of contact hole patterns, There is also a problem that the depth of focus (DOF) is insufficient.

JP 2009-175363 A JP 2009-62422 A JP 2009-191054 A

  The present invention has been made in view of the above-mentioned background, and the object thereof is an actinic ray capable of sufficiently reducing development defects and excellent in depth of focus (DOF), particularly in the formation of contact holes in semiconductor manufacturing. And radiation-sensitive resin composition, and a resist film and a pattern forming method using the same.

[1] (A) A resin containing a repeating unit represented by the following general formula (1), which increases the solubility in an alkali developer by the action of an acid, and (B) generates an acid upon irradiation with actinic rays or radiation. Compound, (C) Actinic ray-sensitive or radiation-sensitive, comprising a repeating unit having two or more polar conversion groups and containing a resin having at least one of a fluorine atom and a silicon atom Resin photosensitive composition.

In general formula (1), R ₁ represents a hydrogen atom, a methyl group, a cyano group, or a halogen atom.
X ₁ and X ₂ each independently represents an alkylene group.
L represents an ether bond, a thioether bond or an ester bond.
When a plurality of X ₁ and L are present, the plurality of X ₁ and the plurality of L may be the same or different.
A represents a group capable of leaving by the action of an acid.
n represents an integer of 1 or more.

[2] The resin (C) contains two or more groups represented by —COO— in the structure represented by the following general formula (KA-1) or (KA-2) as the polar conversion group. The actinic ray-sensitive or radiation-sensitive resin composition as described in [1] above.

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, and when there are a plurality of Z _{ka s} , the plurality of Z _ka are the same. Or Z _ka may be linked to each other 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 represents 0 or 1, and nkb ′ 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 linked to each other. A ring may be formed, and at least two of R _kb3 , R _kb4 and X _kb2 may be linked to each other to form a ring.

[3] The above [2], wherein the repeating unit having two or more polar conversion groups contains a partial structure having two polar conversion groups represented by the following general formula (KY-1): The actinic ray-sensitive or radiation-sensitive resin composition described.

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.
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 general formula (KB-1).

[4] The above [3], wherein the repeating unit having the structure represented by the general formula (KY-1) is a repeating unit having a structure represented by the following general formula (KY-2): An actinic ray-sensitive or radiation-sensitive resin composition.

In general 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 the general formula (KB-1).

[5] The repeating unit having the structure represented by the general formula (KY-2) is a repeating unit having a structure represented by the following general formula (KY-3): An actinic ray-sensitive or radiation-sensitive resin composition.

In general 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 the general formula (KY-2).
R _kb1 , R _kb2 and nkb have the same _meanings as those in the general formula (KB-1).
L _ky represents an alkylene group, an oxygen atom or a sulfur atom.
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.

[6] The active light sensitive or sensitive material according to any one of [1] to [5], wherein the compound (B) is a sulfonium salt having an acid-decomposable group in the cation moiety. Radiation resin composition.

[7] A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6].

[8] A pattern forming method comprising the steps of immersion exposure and development of the resist film according to [7].

The present invention preferably further has the following configuration.
[9] The total number of carbon atoms of the divalent linking group represented by — (X ₁ -L) _n —X ₂ — in the general formula (1) is 1 to 10, ] The actinic-ray-sensitive or radiation-sensitive resin composition as described in any one of [6].
[10] The total number of carbon atoms of the divalent linking group represented by — (X ₁ -L) _n —X ₂ — in the general formula (1) is 2 to 7, ] The actinic ray sensitive or radiation sensitive resin composition as described in any one of [6] and [9].
[11] The total number of carbon atoms of the divalent linking group represented by — (X ₁ -L) _n —X ₂ — in the general formula (1) is 3 to 5, ] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [6], [9], and [10].
[12] The content of the repeating unit represented by the general formula (1) is 10 to 60 mol% with respect to all the repeating units in the resin (A). [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [9] to [11].
[13] The content of the repeating unit represented by the general formula (1) is 20 to 50 mol% with respect to all the repeating units in the resin (A). [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [9] to [12].
[14] The resin (A) according to any one of the above [1] to [6] and [9] to [13], wherein the resin (A) further contains a repeating unit having a lactone group. An actinic ray-sensitive or radiation-sensitive resin composition.
[15] The actinic ray-sensitive property according to any one of [1] to [6] and [9] to [14], wherein the resin (A) does not have an aromatic group. Or a radiation sensitive resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, especially in contact hole pattern formation of semiconductor manufacture, while being able to fully reduce a development defect, the actinic-ray sensitive or radiation sensitive resin composition excellent in the depth of focus (DOF), and this are used. A resist film and a pattern forming method can be provided.

Hereinafter, the present invention will be described in detail.
In addition, in the description of 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 specification, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. . In the present invention, light means actinic rays or radiation.
Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is
(A) a resin containing a repeating unit represented by the following general formula (1) and having increased solubility in an alkaline developer by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(C) It contains a repeating unit having two or more polar conversion groups and contains a resin having at least one of a fluorine atom and a silicon atom.

  According to the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, development defects can be sufficiently reduced and the depth of focus (DOF) can be excellent, particularly in contact hole pattern formation in semiconductor manufacturing.

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

[1] (A) Resin whose solubility in an alkaline developer is increased by the action of an acid The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises a repeating unit represented by the following general formula (1) And a resin (A) whose solubility in an alkaline developer is increased by the action of an acid. The resin (A) is preferably insoluble or hardly soluble in an alkali developer.

In general formula (1), R ₁ represents a hydrogen atom, a methyl group which may have a substituent, a cyano group or a halogen atom.
X ₁ and X ₂ each independently represents an alkylene group.
L represents an ether bond, a thioether bond or an ester bond.
When a plurality of X ₁ and L are present, the plurality of X ₁ and the plurality of L may be the same or different.
A represents a group capable of leaving by the action of an acid.
n represents an integer of 1 or more, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, still more preferably 1 or 2, and most preferably 1.

Examples of the substituent that the methyl group of R ₁ may have include a halogen atom, a hydroxyl group, an alkoxy group, and an acyloxy group. R ₁ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a trifluoromethyl group, a methoxymethyl group or an acetylmethyl group, particularly preferably a hydrogen atom or a methyl group.
The alkylene group for X ₁ and X ₂ is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group or an ethylene group.
_{- (X 1 -L) n -X} 2 - The total number of carbon atoms of the divalent linking group represented by preferably 1 to 10, more preferably 2 to 7, more preferably 3-5.
Specific examples of the divalent linking group represented by — (X ₁ -L) _n —X ₂ — are listed below, but the present invention is not limited thereto. In specific examples, * represents a binding site on the main chain side of the resin, and ** represents a binding site on the A side.

Resin (A) is a resin (acid-decomposable resin) whose solubility in an alkaline developer is increased by the action of an acid, and is a group (hereinafter referred to as an alkali-soluble group) that decomposes in the side chain of the resin by the action of an acid. , Also referred to as “acid-decomposable group”.
More specifically, the repeating unit represented by the general formula (1) has a group (acid-decomposable group) having a structure protected with A as a group in which a carboxyl group is decomposed by the action of an acid. ing.
That is, as described above, A represents a group capable of leaving by the action of an acid, for example, —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR _{39), - C (R 01} ) (R 02) ( can be exemplified _{OR 39)} or the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group (a group in which the hydrogen atom of the carboxyl group is substituted with —C (Rx ₁ ) (Rx ₂ ) (Rx ₃ )). Here, Rx _{1 to} Rx ₃ each independently represents an alkyl group or a cycloalkyl group, and Rx ₂ and Rx ₃ may be bonded to each other to form a cycloalkyl group.
The alkyl group of Rx _{1 to} Rx ₃ may be linear or branched, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t- C1-C4 things, such as a butyl group, are preferable.
The cycloalkyl group of Rx _{1 to} Rx ₃ is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. Is preferred.
Examples of the cycloalkyl group formed by combining Rx ₂ and Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. A polycyclic cycloalkyl group such as is preferable. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to each other to form the cycloalkyl group described above is preferable.

The _{- (X 1 -L) n -X} 2 - 2 divalent linking group represented by _the alkyl group as R 36 _{to R 39} and _R 01 _{to R 02,} cycloalkyl group, aryl group, aralkyl group and alkenyl _group, may be formed by combining _{R 36} and _{R 37} together _ring, alkyl and cycloalkyl group as Rx 1 to Rx _3, and, be formed by combining the Rx ₂ and Rx ₃ are mutually The cycloalkyl group may further have a substituent. Examples of such a further substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, and an alkoxy group. (Preferably having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (preferably having 2 to 6 carbon atoms) and the like are mentioned, and 8 or less carbon atoms are preferable.
Specific examples of the repeating unit having the preferred general formula (1) are shown below, but the present invention is not limited thereto. R ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

  The content of the repeating unit represented by the general formula (1) is preferably 5 to 50 mol%, more preferably 7 to 35 mol%, still more preferably 10 to 25 mol%, based on all repeating units in the resin (A). .

The resin (A) further has a repeating unit having an acid-decomposable group (hereinafter, also referred to as other repeating unit having an acid-decomposable group) other than the repeating unit represented by the general formula (1). It may or may not be.
The acid-decomposable group preferably has a structure protected with a group capable of decomposing and leaving an alkali-soluble group by the action of an acid.
The alkali-soluble group is not particularly limited as long as it is a group that dissociates and becomes an ion in an alkali developer. Preferred alkali-soluble groups include a carboxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol), and a 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.
Specifically, the other repeating unit 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, preferably an alkyl group having 3 or less carbon atoms, More preferred is 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 —COO—Rt— group, and Rt represents an alkylene group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group. In the -COO-Rt- group, the bond on the carbonyl group side is connected to the carbon atom constituting the main chain.
Rx _{1 to} Rx ₃ each independently represents an alkyl group or a cycloalkyl group.
Rx ₂ and Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Specific examples and preferred examples of Rx ₁ to Rx ₃ is a tertiary alkyl ester group (carboxyl group is -C in the repeating unit represented by the general formula _{(1) (Rx 1) (} Rx 2) (Rx 3) And the same as those described in the group).
The alkylene group in the —COO—Rt— group as T and the alkyl group as Rx _{1 to} Rx ₃ may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. (Preferably having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (preferably having 2 to 6 carbon atoms) and the like are mentioned, and 8 or less carbon atoms are preferable.
The cycloalkyl group as Rx ₁ to Rx _3, and, cycloalkyl group which may be formed by combining the Rx ₂ and Rx ₃ are each other may have a substituent, as the substituent, for example, , An alkyl group (preferably having 1 to 4 carbon atoms), an alkylene group in the —COO—Rt— group as T, and an alkyl group as Rx _{1 to} Rx ₃ as a substituent that the alkyl group may have Specific examples can be given.

Although the specific example of repeating units other than the repeating unit represented by General formula (1) which has an acid-decomposable group is shown below, this invention is not limited to this.
In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as specific examples and preferred examples of R ₁₀ in formula (AI-2-1) described later.

  The repeating unit represented by the general formula (AI) is more preferably at least one of the repeating unit represented by the general formula (AI-1) and the repeating unit represented by the general formula (AI-2). preferable.

In the formulas (AI-1) and (AI-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 ′ and R ₃ ′ preferably represent a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a methyl group. Specific examples and preferred examples of the monovalent organic group in R ₉ are the same as those described for R ₉ in formula (AI).

The alkyl group for R ₂ ′ may be linear or branched, and may have a substituent.
The cycloalkyl group for 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 ′ together with the carbon atom is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6.

The alkyl group in R ₄ ′, R ₅ ′, and R ₆ ′ may be linear or branched, and may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.
The cycloalkyl group in R ₄ ′, R ₅ ′, and R ₆ ′ may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

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

In formula (AI-2-1),
R ₃ ′ to R ₅ ′ have the same meaning as in general formula (AI-2).
R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent containing a polar group include a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group itself, or a linear or branched alkyl group or cycloalkyl group having at least one of these groups. Preferably, it is an alkyl group having a hydroxyl group, more preferably a branched alkyl group having a hydroxyl group, and the branched alkyl group is particularly preferably an isopropyl group.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

  In addition, when resin (A) contains the repeating unit represented by the said general formula (AI), as a repeating unit represented by general formula (AI), the repeating unit represented by formula (AI-1) And a combination of repeating units represented by the formula (AI-2) or a combination of different repeating units represented by the formula (AI-1) are preferred.

  Moreover, it is preferable that the repeating unit represented by the said general formula (AI-1) is a repeating unit represented by the following general formula (AI-1-1).

In formula (AI-1-1), R ₁ ′ and R ₂ ′ have the same meanings as in general formula (AI-1). In addition, combined use with the repeating unit whose R < ₂ >'is a methyl group or an ethyl group in Formula (AI-1-1) and the repeating unit of general formula (AI-1) is preferable.

  The total content of repeating units having an acid-decomposable group (that is, the total of repeating units represented by the general formula (1) and other repeating units having an acid-decomposable group) 10-70 mol% is preferable with respect to all the repeating units, More preferably, it is 15-50 mol%.

The resin (A) preferably contains a repeating unit having a lactone group.
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), (LC1-17), especially A preferred lactone structure is (LC1-4). By using a specific lactone structure, LWR 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, the plurality of substituents (Rb ₂ ) may be the same or different. A plurality of substituents (Rb ₂ ) may be bonded to form a ring.

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

Among the units represented by the general formula (AII), the following repeating units are particularly preferable as the repeating unit having a lactone group when Ab is a single bond. In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (A) preferably contains 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, and when there are a plurality of R _{0 s} , R ₀ may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, and when there are a plurality of Z, each Z may be the same or different.
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 the formula (3), and represents an integer of 1 to 5. Preferably 0 or 1.
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. However, when Z is an ester bond, R ₈ is not a group capable of leaving by the action of an acid.

The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group in R ₇ may be substituted. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t -Acetoxy groups such as alkoxy groups such as butoxy group and benzyloxy group, acetyl groups and propionyl groups. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
Preferable chain alkylene group in R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. 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 include lactones represented by general formulas (LC1-1) to (LC1-17). The structure 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.

Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (3) are shown below, but the present invention is not limited thereto.
In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

  The repeating unit having a lactone structure is more preferably a repeating unit represented by the following general formula (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 substituent include an alkoxy group such as a hydroxy group, a methoxy group, and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom.
R ₉ is more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.
Examples of the alkylene group for X include a methylene group and an ethylene group. X is preferably an oxygen atom or a methylene group, and more preferably a methylene group.
When m is 1 or more, at least one R ₉ is preferably substituted at the α-position or β-position of the lactone carbonyl group, particularly preferably at the α-position.

  Specific examples of the repeating unit having a group having a lactone structure represented by General Formula (3-1) are shown below, but the present invention is not limited thereto. In the formula, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

  The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used.

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 (A), More preferably, it is 20-50 mol%, More preferably, it is 30-50 mol%.
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).

Moreover, it is preferable that resin (A) has a repeating unit which has a hydroxyl group or a cyano group as repeating units other than general formula (AI-2-1) and (3-1). 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 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 dihydroxyadamantyl group, and a norbornyl group substituted with a cyano group.
Examples of the repeating unit having the atomic group include 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 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 (AIIa), it is more preferable that _two members out of R ₂ c to R ₄ c are hydroxyl groups and the rest are hydrogen atoms.

  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.

  Resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron withdrawing group at the α-position. It is more preferable to have a repeating unit. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain. Both are preferable, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

  The resin (A) may or may not contain a repeating unit having an alkali-soluble group. However, when it is contained, the content is 1 to 20 mol% with respect to all repeating units in the 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. In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (A) of the present invention may further have a repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability. This can reduce the elution of low molecular components from the resist film to the immersion liquid during immersion exposure. An example of such a repeating unit is a repeating unit represented by the general formula (4).

In General Formula (4), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group (hydroxyl group, cyano group, etc.).
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. Ra ₂ is preferably a hydrogen atom, a methyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include 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. However, the substituent does not contain an acid-decomposable group. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group described above may further have a substituent, and examples of the substituent that may further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. The group can be mentioned.

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

The resin (A) may or may not contain a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group and does not exhibit acid decomposability. 1-40 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 5-20 mol%.
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, in addition to the above repeating structural units, is generally required for dry etching resistance, standard developer suitability, substrate adhesion, profile, and resist. Various repeating structural units can be used for the purpose of adjusting resolving power, heat resistance, sensitivity, and the like, which are various characteristics.

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

  Thereby, performance required for the resin used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, in particular, (1) solubility in coating solvent, (2) film-forming property (glass transition point), Fine adjustments such as (3) alkali developability, (4) film slippage (selection of hydrophilicity / hydrophobicity, alkali-soluble group), (5) adhesion of unexposed part to substrate, (6) dry etching resistance, etc. can be made. .

  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 (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the content molar ratio of each repeating structural unit is dry etching resistance, standard developer suitability, substrate adhesion, profile, It is appropriately set to adjust the resolving power, heat resistance, sensitivity, etc., which are general necessary performances of the resist.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure, the resin (A) does not have an 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, having no aromatic group) The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
Moreover, it is preferable that resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin (C) mentioned later.

  The resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably one in which all repeating units are composed of (meth) acrylate 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 is 20 to 50 mol%, the (meth) acrylate repeating unit having a lactone group is 20 to 50 mol%, and the alicyclic ring is substituted with a hydroxyl group or a cyano group. It is a copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a hydrocarbon structure and further 0 to 20 mol% of another (meth) acrylate-based repeating unit.

The resin (A) of the present invention 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. A solvent that dissolves the product may be mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the 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.

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

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

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

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

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

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

The weight average molecular weight of the resin (A) of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3, as a polystyrene conversion value by GPC method. 000 to 15,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight within the above range, it is possible to prevent heat resistance improvement, dry etching resistance deterioration prevention, developability deterioration, film formation deterioration due to increased viscosity, and the like.
The dispersity (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 2.0. The smaller the molecular weight distribution, the better the resolution and pattern shape, the smoother the side wall of the pattern, and the better the roughness.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the blending amount of the resin (A) in the entire composition is preferably 50 to 99% by mass, more preferably 60 to 95% by mass in the total solid content. It is.
In the present invention, the resin (A) may be used alone or in combination. Or you may use together resin (A) and the other resin which does not correspond to resin (A). In that case, it is preferable that 50 weight% or more of resin (A) exists in all the resins.

[2] (B) Compound that generates acid upon irradiation with actinic ray or radiation The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a compound that generates an acid upon irradiation with 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) methide anion.

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

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

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

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

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

  The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (Preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), aryl Ruoxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) and a cycloalkyl group (preferably C3-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 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

  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 as in the aromatic sulfonate anion, Examples thereof include an alkyl group, a cycloalkyl group, an alkoxy group, and an alkylthio group.

  Examples of the sulfonylimide anion include saccharin anion.

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

  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.

In addition, examples of the non-nucleophilic anion of Z ⁻ include an anion corresponding to an acid represented by the following general formula (I).

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R ₁ and R ₂ , they may be the same or different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents a cyclic organic group.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

General formula (I) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH _{2 CF 3, CH 2 CH 2 CF} 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9, CH ₂ CH ₂ C ₄ F ₉ is mentioned, among which a fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

The alkyl group of R ₁ and R ₂ may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent for R ₁ and R ₂ include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _{15. , C 8 F 17, CH 2} CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which CF ₃ is preferable.
R ₁ and R ₂ are preferably a fluorine atom or CF ₃ .

y is preferably 0 to 4, and more preferably 0. x is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. z is preferably 0 to 8, particularly preferably 0 to 4.
The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these are linked can be mentioned, and a linking group having a total carbon number of 12 or less is preferred. Among these, —COO—, —OCO—, —CO—, —O—, and —SO ₂ — are preferable, and —COO—, —OCO—, and —SO ₂ — are more preferable.

  The cyclic organic group for A is not particularly limited, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (including not only those having an aromatic attribute but also those having no aromatic attribute).

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

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

  Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, and a piperidine ring. Of these, those derived from a furan ring, a thiophene ring, a pyridine ring and a piperidine ring are preferred.

  Further, examples of the cyclic organic group may include a lactone structure, and specific examples thereof may be represented by the general formulas (LC1-1) to (LC1-17) which the above-described resin (A) may have. The lactone structure represented can be mentioned.

  The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear or branched and preferably have 1 to 12 carbon atoms), a cycloalkyl group ( It may be any of monocyclic, polycyclic and spiro rings, preferably having 3 to 20 carbon atoms, aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group (including lactone group). Amide group (including lactam group), urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like. Among them, polar groups such as hydroxy group, methoxy group, ester group (including lactone group), amide group (including lactam group), urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group, development defects, Particularly preferable from the viewpoint of DOF latitude. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

Examples of preferred embodiments of general formula (I) include the following general formulas (Ia) and (Ib). In the formula, Xf, R ₁ , R ₂ , L, A, y, and z have the same meanings as in general formula (I).

  Specific examples of the acid represented by the general formula (I) are shown below.

  Among the specific examples, more preferable acids are shown below.

Examples of the organic group of _{R 201, R 202} and _{R 203} in formula (ZI), for example, a corresponding group in the later-described compounds (ZI-1) ~ (ZI -4).

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

  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, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or a phenylthioarylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. The ring structure may include an oxygen atom, a sulfur atom, a ketone group, an ester bond, and an amide bond.
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.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group, and examples of the alkylene group include a methylene group and an ethylene 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. (For example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group) can be mentioned, and examples of the cycloalkyl group include 3 to 108 carbon atoms. A cycloalkyl 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-C108 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 and alkylthio 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 and arylthio group as R _1c to R _5c are the same as specific examples of the aryl group of _R 1c _{to R 5c.}
Preferably, any one 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 carbon numbers 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.

The ring structure which may be formed by R _5c and R _6c are bonded to each other, bonded R _5c and R _6c are each other a single bond or an alkylene group (methylene group, ethylene group, etc.) by configuring the generally Examples thereof include a carbonyl carbon atom in the formula (I) and a 4-membered ring (particularly preferably a 5- to 6-membered ring) formed together with the carbon atom.

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

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

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

_Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group as R _x and R _y include a group having> C═O at the 2-position of the alkyl group and cycloalkyl group as R _{1c to} R _7c. .

As for the alkoxy group in the alkoxycarbonylalkyl group as R _x and R _y , the same alkoxy group as in R _{1c to} R _5c can be exemplified. Preferably, a C1-C5 linear alkyl group (For example, a methyl group and an ethyl group can be mentioned.

The allyl group as R _x and R _y is not particularly limited, but is an unsubstituted allyl group, or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). An allyl group substituted with is preferable.

The vinyl group as R _x and R _y is not particularly limited, but may be an unsubstituted vinyl group, or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). A substituted vinyl group is preferred.

The ring structure which may be formed by R _5c and R _x are bonded to each other, bonded R _5c and R _x each other a single bond or an alkylene group (methylene group, ethylene group, etc.) by configuring the generally Examples thereof include a 5-membered ring (particularly preferably a 5-membered ring) formed together with the sulfur atom and the carbonyl carbon atom in the formula (I).

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

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

R _{1c to} R _7c , R _x and R _y may further have a substituent. Examples of such a substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, and a nitro group. Group, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonyloxy group, aryl An oxycarbonyloxy group etc. can be mentioned.

Examples of the alkyl group 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. There can be mentioned up to 12 linear or branched alkyl groups.
As said cycloalkyl group, C3-C10 cycloalkyl groups, such as a cyclopentyl group and a cyclohexyl group, can be mentioned, for example.
As said aryl group, C6-C15 aryl groups, such as a phenyl group and a naphthyl group, can be mentioned, for example.

  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.

  As said aryloxy group, C6-C10 aryloxy groups, such as a phenyloxy group and a naphthyloxy group, etc. can be mentioned, for example.

  Examples of the acyl group include carbon such as acetyl group, propionyl group, n-butanoyl group, i-butanoyl group, n-heptanoyl group, 2-methylbutanoyl group, 1-methylbutanoyl group, and t-heptanoyl group. Examples thereof include a linear or branched acyl group having 2 to 12 atoms.

  Examples of the arylcarbonyl group include aryloxy groups having 6 to 10 carbon atoms such as a phenylcarbonyl group and a naphthylcarbonyl 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 aryloxyalkyl group include aryloxy groups having 7 to 12 carbon atoms such as a phenyloxymethyl group, a phenyloxyethyl group, a naphthyloxymethyl group, and a naphthyloxyethyl 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 aryloxycarbonyl group include aryloxycarbonyl groups having 7 to 11 carbon atoms such as phenyloxycarbonyl group and naphthyloxycarbonyl group.

  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 carbonyloxy group and cyclohexyloxycarbonyloxy.

  Examples of the aryloxycarbonyloxy group include aryloxycarbonyloxy groups having 7 to 11 carbon atoms such as phenyloxycarbonyloxy group and naphthyloxycarbonyloxy group.

In the general formula (ZI-3), R _1c , R _2c , R _4c and R _5c each independently represent a hydrogen atom, and R _3c is a group other than a hydrogen atom, that is, an alkyl group, a cycloalkyl group, More preferably, it represents an aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group.

  Specific examples of the cation of the compound represented by the general formula (ZI-2) or (ZI-3) include the following.

  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, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
When there are a plurality of R _{14 s,} each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Represent. These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. These groups may have a substituent.

l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ^- represents a non-nucleophilic anion, 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 of R ₁₃ , R ₁₄ and R ₁₅ include monocyclic or polycyclic cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms), and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, norbornyl, tricyclodecanyl, tetracyclodecanyl, adamantyl and the like, particularly cyclopropyl, cyclopentyl, cyclohexyl, cyclo Heptyl and cyclooctyl are preferred.

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

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

Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms). Examples thereof include a polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

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

The alkoxy group having a monocyclic or polycyclic cycloalkyl group of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, An alkoxy group having a monocyclic cycloalkyl group is preferable. The alkoxy group having a total of 7 or more carbon atoms and having a monocyclic cycloalkyl group is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropoxy, A monocyclic cycloalkyl group which may have the above-mentioned substituent is substituted on an alkoxy group such as sec-butoxy, t-butoxy, iso-amyloxy, etc., and the total carbon number including the substituent is 7 or more. Represents things. Examples thereof include a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, and the like, and a cyclohexylmethoxy group is preferable.
Examples of the alkoxy group having a polycyclic cycloalkyl group having a total carbon number of 7 or more include a norbornyl methoxy group, a norbornyl ethoxy group, a tricyclodecanyl methoxy group, a tricyclodecanyl ethoxy group, a tetracyclo group. A decanyl methoxy group, a tetracyclodecanyl ethoxy group, an adamantyl methoxy group, an adamantyl ethoxy group, etc. are mentioned, A norbornyl methoxy group, a norbornyl ethoxy group, etc. are preferable.
The alkyl group of the alkyl group of R ^14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

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

Examples of the substituent that each 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 alkoxyalkyl. Group, alkoxycarbonyl group, alkoxycarbonyloxy group and the like.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, Examples thereof include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as a cyclohexyloxy group.
Examples of the alkoxyalkyl group include straight chain having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group. Examples thereof include a chain, branched or cyclic alkoxyalkyl group.
Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t Examples thereof include linear, branched or cyclic alkoxycarbonyl groups having 2 to 21 carbon atoms such as butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group 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 straight-chain, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyloxy group and cyclohexyloxycarbonyloxy group.
The ring structure which two R ₁₅ may combine with each other is a 5-membered or 6-membered ring formed by two divalent R ₁₅ together with the sulfur atom in the general formula (ZI-4). Particularly preferred is a 5-membered ring (that is, a tetrahydrothiophene ring), which may be condensed with an aryl group or a cycloalkyl group. This divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, An alkoxycarbonyl group, an alkoxycarbonyloxy group, etc. can be mentioned.
R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two R ^15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).
l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

  Specific examples of the cation of the compound represented by the general formula (ZI-4) include the following.

The acid generator is preferably a sulfonium salt having an acid-decomposable group in the cation moiety. The acid-decomposable group in the cation part of such a sulfonium salt is preferably a group having a structure protected by a group capable of decomposing and leaving an alkali-soluble group by the action of an acid. Examples thereof include a group having a structure protected by a tertiary alkyl ether group, a tertiary alkyl ester group, or a t-butoxycarbonyl group, and among them, a tertiary alkyl ether group and a tertiary alkyl ester group are preferable. The tertiary alkyl ether group is preferably a t-butyloxy group or an amyloxy group. As the tertiary alkyl ester group, a group in which a carboxyl group is substituted with —C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) is preferable.
Wherein _Rx 1 to Rx ₃ is synonymous with _Rx 1 to Rx ₃ described for A in the repeating unit represented by the general formula resin (A) having (1).
Specific examples of the sulfonium cation having an acid-decomposable group are shown below.

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

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).

  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.

The acid generator that generates the acid represented by the general formula (I) corresponding to the compound represented by the general formula (ZV) or (ZVI) is represented by the following general formula (ZVII) or (ZVIII). Can be mentioned.

In general formula (ZVII) or (ZVIII),
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.
Rz represents a structure in which H of the acid represented by the general formula (I) is dissociated, and is represented by the following general formula (I-s).

In the formula, R ₁ , R ₂ , L, A, Xf, x, y, and z are the same as those in the general formula (I). * Represents a bond with a compound residue represented by the general formula (ZVII) or (ZVIII).
Specific examples of the compound residue represented by the general formula (ZVII) or (ZVIII) are shown below.

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

  Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.2 to 40% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, More preferably, it is 1-30 mass%, More preferably, it is 3-20 mass%.

[3] (C) A resin containing a repeating unit having two or more 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 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 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.

The repeating unit (c) is a repeating unit (c *) having two or more polar conversion groups and not having a fluorine atom and a silicon atom, and the resin (C) is a fluorine atom and a silicon atom. It is also preferred to further have a repeating unit having at least one of the following.
Alternatively, the repeating unit (c) has two or more polarity converting groups on one side chain, and at least 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 the repeating unit (c ″) has any one. In this case, the side chain having a polar conversion group and the side chain having at least one of a fluorine atom and a silicon atom are bonded via a carbon atom of the main chain. It is preferable that the α-position is in a positional relationship such as the following formula (4), where B1 is a partial structure having a polar conversion group, and B2 has at least one of a fluorine atom and a silicon atom. Represents a partial structure.

  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 has a 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. Preferred lactone structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1) -14) and (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 repeating unit (c) having two or more polarity conversion groups more preferably contains 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 structures (KA-1-1) to (KA-1-17) are preferable. _{Examples of the} electron withdrawing group include the same groups as those in X _kb1 in the formula (KB-1).

  The repeating unit having a structure represented by the general formula (KY-1) is more preferably a repeating unit having 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 repeating unit having a structure represented by the formula (KY-2) is more preferably a repeating unit having 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) is preferably 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 represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. 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). More specifically, the resin (C) may have a repeating unit having a group selected from the following groups (x) to (z), and the repeating unit includes a fluorine atom and a silicon atom. It may correspond to the said repeating unit (c1) by having at least any one of these.
(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in an 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 , and X ₁ represents a hydrogen atom, —CH ₃ , —F, 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. A group having a lactone structure is preferable.
As 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, the polarity converting group in the repeating unit (c) having two or more polar converting groups is used. A repeating unit having only one is preferable. Like a repeating unit of acrylic acid ester or methacrylic acid ester, the main chain of the resin is decomposed by the action of an alkali developer, and the solubility in the alkali developer increases. A polymerization initiator or a chain transfer agent having a repeating unit to which the group (y) is bonded, or a group (y) whose solubility in an alkaline developer is increased, is introduced at the end of the polymer chain during polymerization. Both are preferred.
The content of the repeating unit having a group (y) that increases the solubility in an alkali developer is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, based on all repeating units in the resin (C). More preferably, it is 5 to 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 is 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 means that (cy1) and (cy2) are an alkali-soluble group or a group that generates 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.
The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (A).

  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).

[4] (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 a fluorine atom and a silicon atom separately from the resin (C). You may further contain resin (CP) which has either. 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 from 1 to 50 mol%, more preferably from 3 to 35 mol%, based on all repeating units in the resin (CP). More preferably, it is 5 to 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.

[5] Solvent Examples of the solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the above-described 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 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3- Methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methyl Preferred is cycloheptanone.

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.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, propylene glycol monomethyl ether, More preferred is ethyl lactate. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and 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 and 2-heptanone are 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 preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.
It is preferable to add a high boiling polar solvent such as γ-butyrolactone or propylene carbonate.

[6] 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.
The amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate group, and the ammonium salt compound having a sulfonate group have at least one alkyl group bonded to a nitrogen atom. Is preferred. The alkyl chain preferably has an oxygen atom 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. _-CH 2 _CH 2 O Among the oxyalkylene group _{-, - CH (CH 3)} CH 2 O- or _-CH 2 _CH 2 _CH 2 O- structure is preferred.
Specific examples of the 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 include those disclosed in U.S. Patent Application Publication No. 2007/0224539. The compounds (C1-1) to (C3-3) exemplified in [0066] can be mentioned, but are not limited thereto.

  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. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.
Moreover, you may contain the compound (D) which basicity increases by the effect | action of an acid as 1 type of a basic compound (you may use together with the above-mentioned basic compound).
The molecular weight of the compound (D) whose basicity is increased by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
The compound (D) is preferably an amine derivative having a group on the nitrogen atom that is eliminated 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 compound (D) preferably has a structure represented by the following general formula (A).

In the general formula (A), Ra independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.
Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
At least two Rb's may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

In general formula (A), the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Ra and Rb are functional groups such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group and oxo group. , An alkoxy group and a halogen atom may be substituted.
As the alkyl group, cycloalkyl group, aryl group or aralkyl group of R (these alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted with the above functional group, alkoxy group or halogen atom) Is
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 1 to 20 carbon atoms) or a derivative thereof formed by bonding of Ra to each other include, for example, pyrrolidine, piperidine, morpholine, 1, 4, 5 , 6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1, 2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2 , 5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene Groups derived from heterocyclic compounds such as indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, groups derived from these heterocyclic compounds A group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino And groups substituted with one or more functional groups such as a group, a morpholino group and an oxo group.

  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 the method described in Protective Groups in Organic Synthesis Fourth Edition. As the most general method, there is a method obtained by reacting a dicarbonate or haloformate with a commercially available amine. In the formula, X represents a halogen atom. The definition and specific examples of Ra and Rb are the same as those described in the general formula (A).

  In the present invention, the 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.

  The composition of the present invention may or may not contain (D) a compound having a group capable of leaving by the action of an acid, but when used, the amount used is that of the composition combined with the basic compound. Based on the total solid content, it is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass.

  The composition ratio of the compound having a group capable of leaving by the action of an acid generator and (D) acid is as follows: acid generator / [(D) compound having a group leaving by the action of acid + basic compound ] (Molar ratio) = 2.5 to 300 is preferable. 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 / [(D) compound having a group capable of leaving by the action of an acid + the following basic compound] (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150. .

[7] Surfactant The actinic ray-sensitive or radiation-sensitive resin composition may further contain a surfactant. When it contains, it contains either fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, surfactant having both fluorine atom and silicon atom), or two or more kinds It is preferable to do.

When the composition of the present invention contains the above-mentioned surfactant, it is possible to give a pattern with less adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. Become.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, Ftop EF301, EF303, (Shin-Akita Kasei Co., Ltd.) )), FLORARD FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac 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 (Toagosei Chemical Co., Ltd.) ), Surflon KH-20, Surflon S-393 (manufactured by AGC Seimi Chemical Co., Ltd.), F EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-18204, FTX-18204 , 230G, 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.). Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

For example, as a commercially available surfactant, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink & Chemicals, Inc.), C ₆ F ₁₃ group Copolymer of acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyethylene)) acrylate (or methacrylate) having a C ₃ F ₇ group And a copolymer of (poly (oxypropylene)) acrylate (or methacrylate).

  In the present invention, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in several combinations.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant, but when it is contained, the content of the surfactant is actinic ray-sensitive or radiation-sensitive. Preferably it is 0.0001-2 mass% with respect to the total solid amount (total quantity except a solvent) of a resin composition, More preferably, it is 0.0005-1 mass%.
On the other hand, by setting the content of the surfactant to 10 ppm or less with respect to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent), the surface uneven distribution of the resin (C) is increased. As a result, the surface of the resist film can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[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 actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a carboxylic acid onium salt, but when it is contained, the content of the carboxylic acid onium salt in the composition is the same as that of the composition. It is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 1 to 7% by mass with respect to the total solid content.

[9] Dissolution-inhibiting compound having a molecular weight of 3000 or less, which decomposes by the action of an acid and increases its solubility in an alkaline developer. Molecular weight 3000, which decomposes by the action of an acid and increases its solubility in an alkaline developer. The following dissolution-inhibiting compound (hereinafter also referred to as “dissolution-inhibiting compound”) contains an acid-decomposable group described in Proceeding of SPIE, 2724,355 (1996) so as not to lower the permeability of 220 nm or less. An alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative is preferred. Examples of the acid-decomposable group and alicyclic structure are the same as those described for the component (B) 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, the phenolic hydroxyl group of the phenol compound is an acid-decomposable group as a dissolution inhibiting compound. Those containing a structure substituted with are preferred. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a dissolution inhibiting compound, but when it is contained, the addition amount of the dissolution inhibiting compound is actinic ray sensitive or radiation sensitive. Preferably it is 3-50 mass% with respect to solid content of a resin composition, More preferably, it is 5-40 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 phenolic compounds having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
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 Formation Method 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 from 30 to 200 nm, from the viewpoint of improving resolution. Are preferably used. 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 film (resist film).
The film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained.

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

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

  For a film formed using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a liquid having a refractive index higher than air (immersion) between the film and the lens when irradiated with actinic rays or radiation. Exposure (immersion exposure) may be performed by filling the medium. 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 film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.

  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 reduced and the surface activity is increased, so that the 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 agent (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 substance or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light, the optical image projected on the film is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

  The electrical resistance of water used as the immersion liquid is preferably 18.3 MQcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably 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 film from directly contacting the immersion liquid between the film formed using the composition of the present invention and the immersion liquid, an immersion liquid hardly soluble film (hereinafter also referred to as “topcoat”). May be provided. The functions necessary for the top coat include applicability to the upper layer of a film formed from an actinic ray-sensitive or radiation-sensitive resin composition, transparency to radiation, particularly radiation having a wavelength of 193 nm, and liquid Examples include poor immersion solubility. It is preferable that the top coat is not mixed with a film formed from the actinic ray-sensitive or radiation-sensitive resin composition and can be uniformly applied to the upper layer of the film.

  From the viewpoint of transparency at 193 nm, the top coat is preferably a polymer that does not contain an aromatic group. 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 resins (C) and (CP) are also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

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

  There is preferably no or small difference in refractive index between the top coat and the immersion liquid. In this case, the resolution can be improved. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water as the immersion liquid. Therefore, the top coat for ArF immersion exposure is close to the refractive index of water (1.44). preferable. From the viewpoint of making the refractive index of the top coat close to the refractive index of the immersion liquid, it is preferable to have fluorine atoms in the top coat. Moreover, it is preferable that a topcoat is a thin film from a viewpoint of transparency and a refractive index.

  The topcoat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Further, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

Examples of the alkali developer in the development step include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, and diethylamine. Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like. Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used, and quaternary ammonium salts typically represented by tetramethylammonium hydroxide aqueous solution (2.38% by mass) While used, Other than this inorganic alkali, primary amines, secondary amines, tertiary amines, alcohol amines, alkaline aqueous solution such as cyclic amines can also 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.

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

<Synthesis of Resin (A-1)>
Under a nitrogen stream, 21.6 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. To this, compounds corresponding to the following repeating units were sequentially added from the left: 6.80 g, 2.36 g, 5.47 g, 7.00 g, and polymerization initiator V601 (Wako Pure Chemical Industries, 1.61 g, 7 for all monomers). 0.0 mol%) in 53.2 g of cyclohexanone 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, then dropwise added to a mixed solution of 420 g of hexane / 180 g of ethyl acetate over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 10 g of Resin (A-1). The weight average molecular weight (Mw) of the obtained resin (A-1) was 8900 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.76. Moreover, the glass transition point (Tg) measured with DSC (product made from TA Instrument) was 150 degreeC.

<Synthesis of Resin (C-1E)>
(Synthesis of raw material monomer (the following 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 sodium hydroxide 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)

(Synthesis of resin (C-1E))
Under a nitrogen stream, 14.03 g of PGMEA was placed in a three-necked flask and heated to 80 ° C. A solution prepared by dissolving 0.69 g of compound (4) (12.06 g) and polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) in 26.06 g of PGMEA was added dropwise thereto 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 620 g of methanol / 70 g of water. The precipitated powder was collected by filtration and dried to obtain polymer (C-1E) (10.01 g). The weight average molecular weight of the obtained polymer was 12000 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.71.

  The following chemical structure is obtained in the same manner as the synthesis of the resin (A-1) and the resin (C-1E) except that the monomer corresponding to each repeating unit is used so as to have a desired composition ratio (molar ratio). And (A-1) to (A-8) having the composition ratio (molar ratio) shown in Table 1, and resin (AB-1) having the following chemical structure and composition ratio (molar ratio) , (AB-2), (C-1E) to (C-5E), and (CP-1E) were synthesized. Further, the weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resins (A-1) to (A-8), (AB-1), and (AB-2) are shown in Table 1 below. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of (-1E) to (C-5E) and (CP-1E) are shown below together with their structures.

<Resin (A)>

<Acid-decomposable resin not corresponding to resin (A)>

<Resin (C)>

<Synthesis of acid generator>
(Synthesis of the following compound (PAG-10))
Triphenylsulfonium iodide 5.07 g (13 mmol), silver acetate 2.25 g (13.5 mmol), acetonitrile 120 mL, and water 60 mL were added and stirred at room temperature for 1 hour. The reaction solution was filtered to obtain a triphenylsulfonium acetate solution.
Under a nitrogen stream, 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride 28.0 g (88.55 mmol), triethylamine 17.92 g (177.1 mmol), diisopropyl ether 210 mL Was cooled with ice, and a mixed solution of 7.56 g (88.2 mmol) of piperidine and 105 mL of diisopropyl ether was added dropwise thereto over 30 minutes. The mixture was stirred for 1 hour under ice cooling, and further stirred at room temperature for 1 hour. The organic layer was washed successively with water, a saturated aqueous ammonium chloride solution and water, and the organic layer was dried over sodium sulfate. The solvent was removed, 140 mL of ethanol and 1400 mg of sodium hydroxide were added, and the mixture was stirred at room temperature for 2 hours. Dilute hydrochloric acid was added to neutralize the reaction solution to obtain a sulfonic acid ethanol solution.
The triphenylsulfonium acetate solution was added to the sulfonic acid solution and stirred at room temperature for 2 hours. 2100 mL of chloroform was added, and the organic layer was washed successively with water, a saturated aqueous ammonium chloride solution, and water. To obtain the following expression (PAG-10) 21.0g (32.76mmol ) as a white solid was purified by column chromatography (SiO _2, chloroform / methanol = mass 5/1).
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.64 (bs, 6H), 3.29 (bs, 2H), 3.64 (bs, 2H), 7.70 (m, 15H)
¹⁹ F-NMR (300 MHz, CDCl ₃ ) δ-111.1 (t, 2F), -114.3 (t, 2F), -119.4 (m, 2F)

  Similarly, the following photoacid generators (PAG-1) to (PAG-9) and (PAG-11) to (PAG-16) were synthesized.

<Preparation of resist composition>
The components shown in Table 1 below are dissolved in the solvent shown in Table 1 below, and filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to form an actinic ray-sensitive or radiation-sensitive composition (positive resist Solution).

  Abbreviations in Table 1 are as follows.

<Basic compound>

<Surfactant>
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: Surflon KH-20 (manufactured by AGC Sey Chemical Co., Ltd.)
W-6: PolyFox PF-6320 (manufactured by OMNOVA solution inc.) (Fluorine-based)

<Solvent>
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: propylene glycol monomethyl ether propionate SL-3: 2-heptanone SL-4: ethyl lactate SL-5: propylene glycol monomethyl ether (PGME)
SL-6: Cyclohexanone SL-7: Propylene carbonate

<Pattern formation>
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a 300 mm diameter silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied, and baked at 100 ° C. for 60 seconds to form a film with a thickness of 100 nm. Using the ArF excimer laser immersion scanner (XT1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection, manufactured by ASML), the contact hole having a hole diameter of 65 nm was obtained. Exposure was made through a 6% halftone mask of a pattern arranged at a pitch of 130 nm. Ultra pure water was used as the immersion liquid. Thereafter, the mixture was heated at 100 ° C. for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsed with pure water, and spin-dried to obtain a resist pattern.

<Development defects>
Using a defect inspection device KLA2360 (trade name) manufactured by KLA-Tencor Corporation, the pixel size of the defect inspection device is set to 0.16 μm, the threshold value is set to 20, and measurement is performed in a random mode. And the number of development defects per unit area (1 cm ² ) was calculated.

<Depth of focus (DOF)>
The exposure amount (Eopt) for reproducing the mask size is obtained by a length-measuring scanning electron microscope (S-9260 manufactured by Hitachi), and the depth of focus (DOF) range that can be reproduced at 65 nm ± 10% is measured at that Eopt. The DOF value was used. Larger values indicate wider and better DOF.

  From the results of Table 2, the resist compositions of Examples containing a resin (A) having a repeating unit represented by the general formula (1) and a fluorine-containing resin having two or more polar conversion groups were used. In this case, compared with the resist compositions of Comparative Examples 1 and 2 that do not contain such a fluorine-containing resin, both the number of development defects and the performance of DOF in contact hole pattern formation are greatly improved, and excellent performance is achieved. You can see that

Claims (8)

(A) a resin containing a repeating unit represented by the following general formula (1) and having increased solubility in an alkaline developer by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(C) An actinic ray-sensitive or radiation-sensitive resin composition containing a repeating unit having two or more polar conversion groups and containing a resin having at least one of a fluorine atom and a silicon atom object.

In general formula (1), R ₁ represents a hydrogen atom, a methyl group which may have a substituent, a cyano group or a halogen atom.
X ₁ and X ₂ each independently represents an alkylene group.
L represents an ether bond, a thioether bond or an ester bond.
When a plurality of X ₁ and L are present, the plurality of X ₁ and the plurality of L may be the same or different.
A represents a group capable of leaving by the action of an acid.
n represents an integer of 1 or more. The resin (C) contains two or more groups represented by —COO— in the structure represented by the following general formula (KA-1) or (KA-2) as the polarity conversion group. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 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, when a plurality are, there is a plurality of Z _ka are respectively the same May be different, or Z _ka may be linked 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 represents 0 or 1, and nkb ′ 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 linked to each other to form a ring _Or at least two of R _kb3 , R _kb4 and X _kb2 may be linked to each other to form a ring. The activity unit according to claim 2, wherein the repeating unit having two or more polar conversion groups contains a partial structure having two polar conversion groups represented by the following general formula (KY-1). A light-sensitive or radiation-sensitive resin composition.

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.
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 general formula (KB-1). The actinic ray according to claim 3, wherein the repeating unit having a structure represented by the general formula (KY-1) is a repeating unit having a structure represented by the following general formula (KY-2). Or radiation sensitive resin composition.

In general 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 the general formula (KB-1). The actinic ray according to claim 4, wherein the repeating unit having a structure represented by the general formula (KY-2) is a repeating unit having a structure represented by the following general formula (KY-3). Or radiation sensitive resin composition.

In general 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 the general formula (KY-2).
R _kb1 , R _kb2 and nkb have the same _meanings as those in the general formula (KB-1).
L _ky represents an alkylene group, an oxygen atom or a sulfur atom.
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 actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the compound (B) is a sulfonium salt having an acid-decomposable group in the cation moiety.   The resist film formed with the actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-6.   A pattern forming method comprising the steps of immersion exposure and development of the resist film according to claim 7.