JP2017116880A - Active ray sensitive or radiation sensitive resin composition, active ray sensitive or radiation sensitive film, pattern formation method and manufacturing method of electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active ray sensitive or radiation sensitive resin composition excellent in roughness property and capable of suppressing generation of application defect and a pattern formation method using the same.SOLUTION: An active ray sensitive or radiation sensitive resin composition contains (A) a resin containing a repeating unit having at least 2 lactone structures and (B) a compound generating acid by irradiation of active ray or radiation and percentage content of a fluorine atom of the compound is 0 to 0.20 based on total mass of the total atom contained in the compound.SELECTED DRAWING: None

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method.

  More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive material suitable for semiconductor manufacturing processes such as IC (Integrated Circuit), circuit boards such as liquid crystal and thermal head, and other photofabrication lithography processes. The present invention relates to a photosensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method.

  Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. The acid generator in the exposed area is decomposed by exposure to generate an acid, and the generated acid is reacted with the reaction catalyst in a post-exposure bake (PEB). Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.

  To reduce the size of semiconductor elements, the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA). Currently, an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. ing. When an ArF excimer laser is used as an exposure light source, a compound having an aromatic group essentially exhibits a large absorption in the 193 nm region. Therefore, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed. (For example, refer to Patent Document 1). Further, as a technique for further increasing the resolving power, a method of filling a high refractive index liquid (hereinafter also referred to as “immersion liquid”) between the projection lens and the sample (ie, immersion method) has been proposed. Further, EUV (Extreme Ultra Violet) lithography and Electron Beam (EB) lithography, which perform exposure with ultraviolet light having a shorter wavelength (13.5 nm), have been proposed.

  In recent years, a negative image forming method including an organic solvent development process in which development is performed using a developer containing an organic solvent (hereinafter also referred to as “organic solvent developer”) is being developed.

Japanese Patent Application Laid-Open No. 2015-160836

  Under such circumstances, in pattern formation using a resist composition, coating defects such as striation, film turbidity, and incomplete coverage of the wafer may occur in the step of applying the resist composition. Therefore, it is expected that a coating defect does not occur and a pattern having excellent resist performance such as line width roughness (LWR) is obtained.

  An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device that have excellent roughness characteristics and can suppress the occurrence of coating defects. It is in providing the manufacturing method of.

  For example, the present invention is as follows.

  [1] (A) a resin containing a repeating unit (a) having at least two lactone structures, and (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and containing the fluorine atom of the compound The rate is an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that is 0 or more and 0.20 or less with respect to the total mass of all atoms contained in the compound.

  [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit (a) having at least two lactone structures is a repeating unit represented by the following general formula (1).

In general formula (1),
Ra represents a hydrogen atom or an alkyl group.
Rb represents a partial structure having two or more lactone structures.

  [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the compound (B) is a compound represented by the following general formula (2).

In general formula (2),
X ₁ and X ₂ each independently represents a fluorine atom or a fluoroalkyl group.
L represents a divalent linking group. When m ≧ 2, each L may be the same or different.
m represents an integer of 0 or more.
Y represents a divalent linking group.
R ₁ represents a hydrogen atom, an alkyl group or a group having a cyclic structure.
M ₁ ⁺ represents a cation.

  [4] The resin (A) further includes a repeating unit (b) having an acid-decomposable group, and the repeating unit (b) is a repeating unit represented by the following general formula (3) [1] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of to [3].

In general formula (3),
R ₁ represents a hydrogen atom or an alkyl group.
Rd _{1 to} Rd ₃ each independently represents a hydrogen atom or an alkyl group.
Z represents a monocyclic structure.

  [5] Further, (C1) a basic compound having a hydrophilic functional group, or (C2) containing at least one ionic compound represented by the following general formulas (4), (5) and (6) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4].

In general formula (4),
X ₄ ⁺ represents a cation.
Rz ₄ represents a cyclic group, an alkyl group or an alkenyl group.

In general formula (5),
X ₅ ⁺ represents a cation.
Rz ₅ represents a cyclic group, an alkyl group or an alkenyl group. However, it is assumed that no fluorine atom is bonded to the carbon atom adjacent to the S atom.

In general formula (6),
X ₆ ⁺ represents a cation.
Rz _6a and Rz _6b each independently represent a cyclic group, an alkyl group or an alkenyl group.
Z ₁ and Z ₂ each independently represents a single bond or a divalent linking group. However, the case where Z ₁ and Z ₂ are both —SO ₂ — is excluded.

  [6] The actinic ray-sensitive or radiation-sensitive resin according to any one of [1] to [5], further comprising (D) a hydrophobic resin containing at least one of a fluorine atom and a silicon atom. Composition.

  [7] The actinic ray-sensitive or radiation-sensitive property according to any one of [1] to [6], wherein the repeating unit (a) is a repeating unit having a structure in which at least two lactone structures are condensed. Resin composition.

  [8] The actinic ray-sensitive or radiation-sensitive resin composition according to [7], wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (7).

In general formula (7),
Ra represents a hydrogen atom or an alkyl group.
Re _{1 to} Re ₈ each independently represents a hydrogen atom or an alkyl group.
Me ₁ represents a single bond or a divalent linking group.
Me ₂ and Me ₃ each independently represent a divalent linking group.

  [9] The actinic ray-sensitive property according to any one of [2] to [6], wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (8): Radiation sensitive resin composition.

In general formula (8),
Ra represents a hydrogen atom or an alkyl group.
M ₁ and M ₂ each independently represents a single bond or a linking group.
Lc ₁ and Lc ₂ each independently represent a group having a lactone structure.

  [10] The actinic ray-sensitive or radiation-sensitive resin composition according to [9], wherein the repeating unit represented by the general formula (8) is a repeating unit represented by the following general formula (9).

In general formula (9),
Ra represents a hydrogen atom or an alkyl group.
Mf ₁ and Mf ₂ each independently represents a single bond or a linking group.
Rf ₁ , Rf ₂ and Rf ₃ each independently represents a hydrogen atom or an alkyl group.
Mf ₁ and Rf ₁ may be bonded to each other to form a ring. Mf ₂ and Rf ₂ or Rf ₃ may be bonded to each other to form a ring.

  [11] A step of applying an actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10] on a substrate to form an actinic ray-sensitive or radiation-sensitive film; A pattern forming method including a step of exposing the formed film and a step of developing the exposed film with a developer.

  [12] The pattern forming method according to [11], wherein the developer is a developer containing an organic solvent.

  [13] A method for manufacturing an electronic device including the pattern forming method according to [11] or [12].

  [14] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10].

  According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device that have excellent roughness characteristics and are capable of suppressing the occurrence of coating defects. It is possible to provide a manufacturing method.

Hereinafter, preferred embodiments of the present invention will be described in detail.
In the description of groups and atomic groups in this specification, when substitution or non-substitution is not clearly indicated, both those having no substituent and those having a substituent are included. For example, an “alkyl group” that does not explicitly indicate substitution or unsubstituted includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). I will do it.

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

  In addition, the term “exposure” in the present specification is not limited to exposure to far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light) and the like represented by mercury lamps and excimer lasers. It is also assumed that drawing by particle beams such as.

  In this specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”. “(Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

  In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

<Actinic ray-sensitive or radiation-sensitive resin composition>
First, the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “composition”) according to the present invention will be described. This composition may be used for negative development or positive development. That is, this composition may be used for development using a developer containing an organic solvent, or may be used for development using an alkali developer.

  The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention includes a resin (A) containing a repeating unit (a) having at least two lactone structures, and a compound that generates an acid upon irradiation with actinic rays or radiation. The fluorine atom content of this compound is 0 to 0.20 with respect to the total mass of all atoms contained in this compound (hereinafter referred to as photoacid generator (B). It is also called). Although described in detail later, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is obtained by combining the above-described hydrophilic photoacid generator (B) with the above-described hydrophilic resin (A). The occurrence of coating defects can be suppressed.

In addition, the composition is decomposed by the action of the acid diffusion controller (C), the hydrophobic resin (D), the solvent, the surfactant, the carboxylic acid onium salt, and the acid to increase the solubility in an alkaline developer. , A dissolution inhibiting compound having a molecular weight of 3000 or less, and other additives may be further included.
Hereinafter, each of these components will be described in order.

[1] Resin (A) containing repeating unit (a) having at least two lactone structures
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a resin (A) containing a repeating unit having at least two lactone structures. The resin (A) contains a repeating unit (a) having at least two lactone structures (hereinafter also referred to as “repeating unit (a)”). The resin (A) further includes a repeating unit (b) having a group capable of decomposing by the action of an acid to generate an alkali-soluble group in the main chain or side chain of the resin, or both of the main chain and side chain. The repeating unit (c) having a lactone structure different from (a) or other repeating units described later may be included.
[1-1] Repeating unit (a) having at least two lactone structures
The resin (A) contains a repeating unit (a) having at least two lactone structures (hereinafter also referred to as “repeating unit (a)”).

  The at least two lactone structures may be, for example, a structure in which at least two lactone structures are condensed, or a structure in which at least two lactone structures are connected by a single bond or a linking group. Good.

  The lactone structure of the repeating unit (a) is not particularly limited, but a 5- to 7-membered ring lactone structure is preferable, and other ring structures are condensed to form a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure. A ring is preferable.

  The lactone structure is more preferably a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17). More preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17). By using a specific lactone structure, LWR and development defects are improved.

The lactone structure may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. Here, the acid-decomposable group represents a group that decomposes by the action of an acid to generate an alkali-soluble group, and has the same meaning as the acid-decomposable group described later.

n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

  The repeating unit having at least two lactone structures (hereinafter also referred to as “repeating unit (a)”) is preferably a repeating unit represented by the following general formula (1).

In general formula (1),
Ra represents a hydrogen atom or an alkyl group.
Rb represents a partial structure having two or more lactone structures.

  The alkyl group of Ra 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 of Ra 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-butoxy group, alkoxy group such as benzyloxy group, acetyl group, etc. And acetoxy group such as propionyl group. Ra is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

  Examples of the lactone structure possessed by the Rb partial structure include the lactone structures described above.

  The partial structure having two or more lactone structures of Rb is preferably, for example, a structure in which at least two lactone structures are connected by a single bond or a linking group, and a structure in which at least two lactone structures are condensed. .

  The repeating unit (a1) having a structure in which at least two lactone structures are condensed, and the repeating unit (a2) having a structure in which at least two lactone structures are connected by a single bond or a linking group are described below. Each will be described.

(1) Repeating unit (a1) having a structure in which at least two lactone structures are condensed
The structure in which at least two lactone structures are condensed is preferably a structure in which two or three lactone structures are condensed, and is a structure in which two lactone structures are condensed. Is more preferable.

  Examples of the repeating unit having a structure in which at least two lactone structures are condensed (hereinafter also referred to as “repeating unit (a1)”) include a repeating unit represented by the following general formula (7).

In general formula (7),
Ra has the same meaning as Ra in the general formula (1).
Re _{1 to} Re ₈ each independently represents a hydrogen atom or an alkyl group.
Me ₁ represents a single bond or a divalent linking group.
Me ₂ and Me ₃ each independently represent a divalent linking group.

For example, the alkyl group of Re _{1 to} Re ₈ preferably has 5 or less carbon atoms, and more preferably 1 carbon atom.
The alkyl group having 5 or less carbon atoms of Re _{1 to} Re ₈ is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, or an isopentyl group. Group, s-pentyl group, t-pentyl group and the like.

Re _{1 to} Re ₈ are preferably hydrogen atoms.

Examples of the divalent linking group of Me ₁ include an alkylene group, a cycloalkylene group, —O—, —CO—, —COO—, —OCO—, and a group obtained by combining two or more of these groups. It is done.

For example, the alkylene group of Me ₁ preferably has 1 to 10 carbon atoms. Moreover, it is more preferable that it is C1-C2, and as a C1-C2 alkylene group, a methylene group or ethylene group is preferable, for example.

The alkylene group of Me ₁ may be linear or branched. For example, methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane -1,3-diyl group, propane-2,2-diyl group, pentane-1,5-diyl, hexane-1,6-diyl group and the like.

The cycloalkylene group of Me ₁ preferably has, for example, 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms.

Examples of the cycloalkylene group of Me ₁ include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and a cyclodecylene group.

As the divalent linking group of Me ₁ , the group in which two or more groups are combined includes, for example, a group in which an alkylene group and —COO— are combined, and a group in which —OCO— and an alkylene group are combined. preferable. Moreover, the group which combined the said 2 or more group has more preferable the group which combined the methylene group and -COO- group, and the group which combined the -COO- group and the methylene group.

Examples of the divalent linking group of Me ₂ and Me ₃ include an alkylene group and —O—. The divalent linking group of Me ₂ and Me ₃ is preferably a methylene group, an ethylene group or —O—, more preferably —O—.

  The monomer corresponding to the repeating unit (a1) can be synthesized, for example, by the method described in JP-A-2015-160836.

Specific examples of the repeating unit (a1) are shown below, but the present invention is not limited thereto. In the following formulas, R ⁹ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

(2) Repeating unit (a2) having a structure in which at least two lactone structures are linked by a single bond or a linking group
The structure in which at least two lactone structures are connected by a single bond or a linking group is preferably a structure in which 2 to 4 lactone structures are connected by a single bond or a linking group. It is more preferable that the structure is connected by a single bond or a linking group.

Examples of the linking group include the same groups as those exemplified as the linking group for M ₂ in formula (8) described later.

  A repeating unit having a structure in which two or more lactone structures are linked by a single bond or a linking group (hereinafter also referred to as “repeating unit (a2)”) is represented by, for example, the following general formula (8). Repeat units are mentioned.

In general formula (8),
Ra has the same meaning as Ra in the general formula (1).
M ₁ and M ₂ each independently represents a single bond or a linking group.
Lc ₁ and Lc ₂ each independently represent a group having a lactone structure.
Examples of the linking group for M ₁ include an alkylene group, a cycloalkylene group, —O—, —CO—, —COO—, —OCO—, and a group obtained by combining two or more of these groups.

The alkylene group for M ₁ preferably has, for example, 1 to 10 carbon atoms.

The alkylene group of M ₁ may be linear or branched. For example, a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, propane -1,3-diyl group, propane-2,2-diyl group, pentane-1,5-diyl, hexane-1,6-diyl group and the like.

The M ₁ cycloalkylene group preferably has, for example, 5 to 10 carbon atoms.

Examples of the cycloalkylene group represented by M ₁ include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and a cyclodecylene group.

The group in which two or more groups are combined as the linking group for M ₁ is preferably, for example, a group in which an alkylene group and —COO— are combined, or a group in which —OCO— and an alkylene group are combined. Moreover, the group which combined the said 2 or more group has more preferable the group which combined the methylene group and -COO- group, and the group which combined the -COO- group and the methylene group.

Examples of the linking group for M ₂ include the same groups as those exemplified for the linking group for M ₁ .

The lactone structure possessed by Lc ₁ is, for example, preferably a 5- to 7-membered ring lactone structure, and other ring structures are condensed in the form of forming a bicyclo structure or a spiro structure on the 5- to 7-membered ring lactone structure. preferable. The lactone structure is more preferably a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-17). More preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17). .

The lactone structure possessed by Lc ₁ may contain a substituent. Examples of the substituent that the lactone structure that Lc ₁ has may include the same substituent as the substituent (Rb2) of the lactone structure described above.

Lactone structure Lc ₂ has, for example, include the same structure as the lactone structure listed in lactone structure Lc ₁ has.

  The repeating unit (a2) is preferably a repeating unit represented by the following general formula (9) as the repeating unit represented by the general formula (8).

In general formula (9),
Ra has the same meaning as Ra in the general formula (1).
Mf ₁ and Mf ₂ each independently represents a single bond or a linking group.
Rf ₁ , Rf ₂ and Rf ₃ each independently represents a hydrogen atom or an alkyl group.
Mf ₁ and Rf ₁ may be bonded to each other to form a ring. Mf ₂ and Rf ₂ or Rf ₃ may be bonded to each other to form a ring.

The linking group of Mf _{1 has} the same meaning as the linking group of M _{1 in} the general formula (8).

The linking group of Mf _{2 has} the same meaning as the linking group of M _{2 in} the general formula (8).

Alkyl group of Rf ₁ include, for example, an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms of Rf ₁ is preferably a methyl group or an ethyl group, and more preferably a methyl group. The alkyl group of Rf ₁ may have a substituent. Examples of the substituent that the alkyl group of Rf ₁ may have include an alkoxy group such as a hydroxy group, a methoxy group, and an ethoxy group, a cyano group, and a halogen atom such as a fluorine atom.

Alkyl group Rf ₂ and Rf ₃ has the same meaning as the alkyl group of Rf _1.

Mf ₁ and Rf ₁ may be bonded to each other to form a ring. The structure in which Mf ₁ and Rf ₁ are bonded to each other to form a ring is, for example, a lactone structure represented by the general formulas (LC1-13), (LC1-14), and (LC1-17) in the lactone structure described above. Is mentioned.

Mf ₂ and Rf ₂ or Rf ₃ may be bonded to each other to form a ring.
The structure in which Mf ₂ and Rf ₂ are bonded to each other to form a ring is, for example, a lactone structure represented by the general formulas (LC1-7), (LC1-8), and (LC1-15) in the lactone structure described above. Is mentioned.
Examples of the structure in which Mf ₂ and Rf ₃ are bonded to each other to form a ring include lactone structures represented by general formulas (LC1-3) to (LC1-6) in the lactone structure described above.

Specific examples of the repeating unit (a2) are shown below, but the present invention is not limited thereto.

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

  The content of the repeating unit having at least two lactone structures is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, still more preferably 30 to 50 mol%, based on all repeating units in the resin (A). .

  In order to enhance the effect of the present invention, two or more kinds of repeating units having at least two lactone structures can be used in combination. When two or more kinds of repeating units having at least two lactone structures are contained, the total content of the repeating units having at least two lactone structures is preferably in the above range.

[1-2] Repeating unit having acid-decomposable group (b)
The resin (A) is a group (hereinafter also referred to as “acid-decomposable group”) that is decomposed by the action of an acid to generate an alkali-soluble group in the main chain or side chain of the resin or in both the main chain and the side chain. ) (Hereinafter also referred to as “acid-decomposable repeating unit”) (b).
The resin (A) is preferably insoluble or hardly soluble in an alkali developer.

  The acid-decomposable group preferably has a structure protected with a group capable of decomposing and leaving an alkali-soluble group by the action of an acid.

  Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.

  Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.

  A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.

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

  The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

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

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

T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least 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.
Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, A polycyclic cycloalkyl group such as an adamantyl group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group is preferable.

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

  The content of the repeating units having an acid-decomposable group is preferably 10 to 70 mol%, more preferably 40 to 70 mol%, based on all repeating units in the resin (A).

Although the specific example of the repeating unit which has a preferable acid-decomposable group is shown below, this invention is not limited to this.
In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. p represents 0 or a positive integer.

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

In formulas (I) and (II)
R ₁ and R ₃ each independently 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 monovalent organic group.
R ₂ , R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
R ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The alkyl group in R ₂ may be linear or branched, and may have a substituent.
The cycloalkyl group in R ₂ may be monocyclic or polycyclic and may have a substituent.
R ₂ is preferably an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.

  R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 8 or less, more preferably 3 to 7, and still more preferably 5 or 6 It is.

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

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

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

  Examples of the repeating unit represented by the general formula (I) include a repeating unit represented by the following general formula (3).

In general formula (3),
R ₁ has the same meaning as _{R 1} of formula (I).
Rd _{1 to} Rd ₃ each independently represents a hydrogen atom or an alkyl group.
Z represents a monocyclic structure.

Alkyl group Rd ₁ ~ Rd _3, for example, include an alkyl group having 1 to 4 carbon atoms. Alkyl group having 1 to 4 carbon atoms Rd ₁ ~ Rd ₃ is preferably a methyl group.

  Examples of the monocyclic structure of Z include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. The monocyclic cycloalkyl group preferably has 8 or less carbon atoms. The monocyclic cycloalkyl group having 8 or less carbon atoms of Z is preferably a cyclopentyl group or a cyclohexyl group.

  Moreover, as a repeating unit represented by general formula (I), the repeating unit represented by the following general formula (1-a) is mentioned, for example.

In the formula, _{R 1} and _{R 2} have the same meanings as those in formula (I).
The repeating unit represented by the general formula (II) is preferably a repeating unit represented by the following general formula (II-1).

In formula (II-1),
R _{3 to} R ₅ have the same meaning as in general formula (II).
R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent containing a polar group include a linear or branched alkyl group or cycloalkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, and preferably a hydroxyl group. It is an alkyl group. As the branched alkyl group, an isopropyl group is particularly preferable.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

  The resin (A) is a resin containing at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably. In another embodiment, a resin containing at least two kinds of repeating units represented by the general formula (I) as the repeating unit represented by the general formula (AI) is more preferable.

  Preferred combinations when the resin (A) uses an acid-decomposable repeating unit are listed below. In the following formula, each R independently represents a hydrogen atom or a methyl group.

[1-3] Repeating unit (c) having a lactone structure different from repeating unit (a)
The resin (A) may contain a repeating unit having a lactone structure in addition to the unit represented by the repeating unit (a).

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

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

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

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

  Examples of the repeating unit (c) having a lactone structure different from the particularly preferable repeating unit (a) include the following repeating units. By selecting an optimal lactone structure, the pattern profile and the density dependency are improved.

The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
The content of the repeating unit having a lactone structure other than the repeating unit represented by the repeating unit (a) is preferably from 15 to 60 mol%, more preferably from 20 to 50 mol%, still more preferably based on all repeating units in the resin. Is 30-50 mol%. When two or more kinds of repeating units having a lactone structure other than the repeating unit represented by the repeating unit (a) are contained, the total of the repeating units having a lactone structure other than the repeating unit represented by the repeating unit (a) The content rate is preferably in the above range.
The resin (A) preferably has a repeating unit having a hydroxyl group or a cyano group other than the repeating units (a) to (c) described above. This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, a structure represented by the following general formula is preferred.

  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 include the repeating unit disclosed in paragraph 0340 of US Patent Publication No. 2012/0135348, but the present invention is not limited thereto.

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

  As for content of the repeating unit which has an alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.

  Specific examples of the repeating unit having an alkali-soluble group include the repeating unit disclosed in paragraph 0344 of US Patent Publication No. 2012/0135348, but the present invention is not limited thereto.

  The resin (A) of the present invention further has an alicyclic hydrocarbon structure that does not have a polar group (for example, the alkali-soluble group, hydroxyl group, cyano group, etc.) and has a repeating unit that does not exhibit acid decomposability. it can. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In the general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.

Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group. Groups. The preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, more preferably a cyclopentyl group or a cyclohexyl group.

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

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

  These alicyclic hydrocarbon groups may have a substituent. 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. 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 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 group in which the hydrogen atom is substituted 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) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. The content of is preferably from 1 to 40 mol%, more preferably from 2 to 20 mol%, based on all repeating units in the resin (A).

  Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability include the repeating unit disclosed in paragraph 0354 of US Published Patent Application No. 2012/0135348. However, the present invention is not limited to these.

  Resin (A) used in the composition of the present invention has a dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolving power, which is a general necessary characteristic of resist, in addition to the above repeating structural units. It can have various repeating structural units for the purpose of adjusting heat resistance, sensitivity and the like.

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

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

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

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

  In the resin (A) used in the composition of the present invention, the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required performance of the resist. It is appropriately set to adjust the resolving power, heat resistance, sensitivity and the like.

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

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

  When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (A) further has a hydroxystyrene-based repeating unit. It is preferable. More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such as a (meth) acrylic acid tertiary alkyl ester.

  Examples of the repeating unit having a preferred acid-decomposable group based on hydroxystyrene include, for example, t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, a repeating unit of (meth) acrylic acid tertiary alkyl ester, and the like. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

[1-5] Synthesis method of resin (A)
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 the polymerization is performed by heating, 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, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the photosensitive composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

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

  In order to prevent the resin from aggregating after the preparation of the composition, for example, as described in JP-A-2009-037108, the synthesized resin is dissolved in a solvent to form a solution. A step of heating at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours may be added.

  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 to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

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

  Moreover, the resin (A) of the present invention may be used alone or in combination. In this case, two or more kinds of resins containing a repeating unit (a) having at least two lactone structures may be used, and a resin containing a repeating unit (a) within a range not impairing the effects of the present invention, You may use together with other resin which does not contain the repeating unit (a).

  In the present invention, the blending ratio of the resin (A) in the entire composition is preferably from 30 to 99 mass%, more preferably from 60 to 95 mass%, based on the total solid content.

  Although the specific example of resin (A) is given to the following, this invention is not limited to these.

[2] Compound (B) that generates acid upon irradiation with actinic rays or radiation
The composition according to the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation, and the content of fluorine atoms in the compound is 0 or more with respect to the total mass of all atoms contained in the compound. The compound contains 0.20 or less (hereinafter also referred to as “photoacid generator (B)”).

  When the resin in the actinic ray-sensitive or radiation-sensitive resin composition is a hydrophilic resin containing a repeating unit having at least two lactone structures, the present inventors have described specific hydrophilic properties described in detail below. It has been found that the occurrence of coating defects can be suppressed by combining a suitable photoacid generator (B).

  The present inventors also have an actinic ray sensitivity in which a hydrophilic resin containing a repeating unit having at least two lactone structures and a specific hydrophilic photoacid generator (B) described in detail below are combined. Or when a radiation sensitive resin composition is applied to immersion exposure, it has discovered that immersion liquid followability improves. The reason for this is not always clear, but the present inventors speculate as follows. That is, the present inventors combine a specific hydrophilic photoacid generator (B) with a resin having a hydrophilic structure, and particularly when the immersion medium is water, the applied actinic ray-sensitive property. Alternatively, in the radiation-sensitive resin composition, hydrophobic compounds are more unevenly distributed on the surface, thereby improving the contact angle of the actinic ray-sensitive or radiation-sensitive film surface with respect to water and improving the immersion liquid following property. I believe that it is possible.

  The photoacid generator (B) has a fluorine content of 0.20 or less with respect to the total mass of all atoms contained in this compound. All the contained atoms include hydrogen atoms contained in the photoacid generator (B). The fluorine content of the photoacid generator (B) is preferably 0.17 or less, and more preferably 0.10 or less. If it carries out like this, the shape of the pattern formed using the composition concerning this invention will become still better. Further, the fluorine content of the photoacid generator (B) is 0 or more.

  A photo-acid generator (B) may be used individually by 1 type, and may be used in combination of 2 or more type. When two or more photoacid generators (B) are used in combination, the fluorine content of the photoacid generator (B) is equal to the fluorine content of each photoacid generator (B). ) And the values calculated by multiplying by the blending ratio are added to each other.

  The photoacid generator (B) may be a compound represented by the following general formula (2).

In general formula (2),
X ₁ and X ₂ each independently represents a fluorine atom or a fluoroalkyl group.
L represents a divalent linking group. When m ≧ 2, each L may be the same or different.
m represents an integer of 0 or more.
Y represents a divalent linking group.
R ₁ represents a hydrogen atom, an alkyl group or a group having a cyclic structure.
M ₁ ⁺ represents a cation.

The fluoroalkyl group as X ₁ and X ₂ preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, the fluoroalkyl group as X ₁ and X ₂ is preferably a perfluoroalkyl group.

X ₁ and X ₂ are preferably a fluorine atom or a perfluoroalkyl group.
Specific examples of X ₁ and X ₂ are 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 and CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which a fluorine atom or CF ₃ is preferable. In particular, it is preferable that both X ₁ and X ₂ are fluorine atoms.

L of is not particularly restricted but includes divalent linking group, -COO -, - OCO -, - CO -, - O -, - S -, - SO -, - SO 2 -, an alkylene group, a cycloalkylene group, or Alkenylene groups can be mentioned. Among these, —COO—, —OCO—, —CO—, —O—, —SO ₂ — and an alkylene group are preferable, and —COO—, —OCO—, —SO ₂ — and an alkylene group are more preferable. The alkylene group as L may be linear or branched. In addition, the alkylene group, cycloalkylene group or alkenylene group may be substituted with a fluorine atom or the like.
m is preferably 0 to 10, more preferably 0 to 8, and still more preferably 0 to 4.

Y represents a divalent linking group. The divalent linking group for Y is, for example, —CO—, —COO—, —OCO—, —CON (R ₂ ) —, —O—, —S—, —SO—, —SO ₂ —, —OSO. ₂ -, - _SO 2 O-, or a combination of these two or more thereof. Y is preferably —CO—, —COO— or —OCO—. R ₂ represents a hydrogen atom, an alkyl group, or a group having a cyclic structure.

Y is also preferably represented by —CON (R ₂ ) —. That is, the compound represented by the general formula (2) is also preferably represented by the following general formula (I-AM).

_X 1 in the general formula _{(I-AM), X 2} , L, m, R 1, R 2 and _M ^{1 +} is the same meaning as in general formula (2).
R ₁ and R ₂ in general formula (2) and general formula (I-AM) each independently represent a hydrogen atom, an alkyl group, or a group having a cyclic structure.

The alkyl group may be linear or branched, and preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms. Specific examples of R ₁ and R ₂ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-dodecyl. Group, 2-ethylhexyl group, isopropyl group, sec-butyl group, t-butyl group, iso-amyl group, etc., among which methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group Group, t-butyl group is preferred.

  The alkyl group may have a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, a methoxy group, and an ethoxy group. Group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group and other alkoxy groups, methoxycarbonyl group, ethoxycarbonyl group and other alkoxycarbonyl groups, formyl group, acetyl group, benzoyl group and other acyl groups, acetoxy group, butyryloxy Examples include an acyloxy group such as a group, and a carboxy group.

Examples of the group having a cyclic structure as R ₁ and R ₂ include a group having a monocyclic structure (preferably having 3 to 12 carbon atoms) and a group having a polycyclic structure (preferably having 4 to 25 carbon atoms). be able to.

  Examples of the group having a monocyclic structure include a monocyclic hydrocarbon group, a monocyclic heterocyclic group, and an alkyl group containing at least one of these.

  Examples of the monocyclic hydrocarbon group include a monocyclic alkyl group and a monocyclic aryl group.

As the monocyclic alkyl group, those having 3 to 10 carbon atoms are preferable. Specific examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecanyl group, a cyclopentenyl group, a cyclohexenyl group, and a cyclooctadienyl group. A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are particularly preferable.
Examples of the monocyclic aryl group include a substituted or unsubstituted phenyl group.

  Examples of the monocyclic heterocyclic group include a saturated heterocyclic group and an unsaturated heterocyclic group, and those having 5 to 10 carbon atoms are preferable. Examples of the saturated heterocyclic group include 1-piperidyl group, 4-piperidyl group, 4-morpholinyl group, 1,3-dioxolan-2-ylmethyl group, azepan-2-one-1-yl group and the like. Examples of the unsaturated heterocyclic group include a pyrrole group, a furan group, and a thiophene group.

  As the alkyl group containing at least one of a monocyclic hydrocarbon group and a monocyclic heterocyclic group, any hydrogen atom of an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms) may be monocyclic A group substituted by at least one of a cyclic hydrocarbon group and a monocyclic heterocyclic group (for example, a monocyclic hydrocarbon or monocyclic heterocyclic group such as a cyclopentylmethyl group, a cyclohexylmethyl group, a cyclooctylmethyl group, etc. (Alkyl group substituted with) can be preferably mentioned.

  The group having a polycyclic structure is a group selected from (i) a polycyclic hydrocarbon group, (ii) a polycyclic heterocyclic group, (iii) a monocyclic hydrocarbon group and a monocyclic heterocyclic group. (Iv) an alkyl group containing two or more groups selected from a monocyclic hydrocarbon group and a monocyclic heterocyclic group, (v) a polycyclic hydrocarbon group or a polycyclic hetero group Examples thereof include an alkyl group containing a cyclic group.

  The polycyclic hydrocarbon group and the monocyclic hydrocarbon group may be an aliphatic group or an aromatic group, and particularly preferably an alicyclic hydrocarbon group.

Specifically, the polycyclic hydrocarbon group preferably has 10 to 20 carbon atoms. Specific examples of the polycyclic hydrocarbon group include bicyclo [4.3.0] nonanyl group, naphthalenyl group, decahydronaphthalenyl group, 1,2,3,4-tetrahydronaphthalenyl group, tricyclo [5]. .2.1.0 (2,6)] decanyl group, bornyl group, isobornyl group, norbornyl group, adamantyl group, noradamantyl group, 1,7,7-trimethyltricyclo [2.2.1.0 ^{2, 6} ] heptanyl group, 3,7,7-trimethylbicyclo [4.1.0] heptanyl group and the like, and norbornyl group, adamantyl group and noradamantyl group are particularly preferable.

  As the polycyclic heterocyclic group, those having 10 to 20 carbon atoms are preferable. Specific examples of the polycyclic heterocyclic group include an indole group and a carbazole group.

  A group consisting of two or more groups selected from a monocyclic hydrocarbon group and a monocyclic heterocyclic group, and two or more groups selected from a monocyclic hydrocarbon group and a monocyclic heterocyclic group Examples of the monocyclic hydrocarbon group and monocyclic heterocyclic group in the alkyl group include those described above.

  The alkyl group containing two or more groups selected from a monocyclic hydrocarbon group and a monocyclic heterocyclic group is any two alkyl groups having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms). Preferable examples include groups in which the above hydrogen atoms are substituted with a group selected from a monocyclic hydrocarbon group and a monocyclic heterocyclic group.

  As the alkyl group containing a polycyclic hydrocarbon group or a polycyclic heterocyclic group, an alkyl group substituted with the above polycyclic hydrocarbon group is preferable. For example, an adamantylmethyl group, norbornylmethyl group, decahydro And an alkyl group substituted with a polycyclic hydrocarbon or a polycyclic heterocyclic group, such as a naphthylmethyl group).

R ₁ and R ₂ may be bonded to each other to form a ring. The ring may be a monocyclic structure or a polycyclic structure. Examples of the ring structure that can be formed by R ₁ and R ₂ include a monocyclic structure such as a piperidine ring, and a polycyclic structure such as a decahydroquinoline ring and a decahydroisoquinoline ring.

Group having a cyclic structure as R _1, R _2, and the ring which R ₁ and R ₂ are bonded to each other to form may have a substituent, as such further substituents Is a hydroxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), nitro group, cyano group, amide group, sulfonamido group, methyl group, ethyl group, propyl group, n-butyl group, sec- Alkyl groups such as butyl group, hexyl group, 2-ethylhexyl group and octyl group, alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group, methoxycarbonyl group, ethoxycarbonyl group and the like Acyl groups such as alkoxycarbonyl groups, formyl groups, acetyl groups, and benzoyl groups, acyl groups such as acetoxy groups and butyryloxy groups Shi group and a carboxy group.

R ₁ and R ₂ are bonded to each other to form a ring, or R ₁ is an alkyl group having 5 or more carbon atoms, or a group having a cyclic structure (preferably having 5 or more carbon atoms). preferably, either R ₁ and R ₂ combine to form a ring together, or, R ₁ is a cyclic structure is more preferably a group having a (number of carbon atoms is preferably 5 or more), and R ₁ More preferably, R ₂ is bonded to each other to form a polycycle, or R ₁ is a group having a polycyclic structure. Further, when R ₁ is a group having a cyclic structure, R ₂ is also preferably a group having a cyclic structure.

Below, the preferable example of the anion part of the compound represented by General formula (2) is enumerated as a structure of a corresponding acid. In specific examples, X ₁ and X ₂ each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

As the cation represented by M ₁ ^+, those represented by the following general formula (ZI) are preferable.

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

The organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not particularly limited, and examples thereof include corresponding groups in the cation described in paragraphs 0174 to 0227 of JP2012-093733A.

A cation having a plurality of structures represented by the general formula (ZI) may also be used. For example, at least one of the general formula (ZI) expressed in cation in R ₂₀₁ to R _203, at least one coupling structure of the general formula Another cation represented by (ZI) R ₂₀₁ to R ₂₀₃ It may be a compound.

  Specific examples of the photoacid generator (B) of the present invention include the compounds described in paragraphs 0232 to 0239 of JP2012-093733A, but the present invention is not limited thereto.

  The content of the photoacid generator (B) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and still more preferably 1 to 23, based on the total solid content of the composition. % By mass, particularly preferably 3 to 20% by mass.

[3] Acid diffusion controller (C)
The composition of the present invention may further contain an acid diffusion controller (C). The acid diffusion controller (C) functions as a quencher that traps the acid generated from the photoacid generator by exposure, and plays a role in controlling the acid diffusion phenomenon in the film.

  The acid diffusion inhibitor (C) may be, for example, a basic compound. The basic compound is preferably a compound having a stronger basicity than phenol. Moreover, this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound. Although the nitrogen-containing basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(5) can be used.

  Moreover, the composition of this invention may also contain the ionic compound classified into the following (6) as an acid diffusion control agent in another form.

(1) Basic compound (C1) having a hydrophilic functional group
The basic compound (C1) having a hydrophilic functional group is preferably a compound represented by the following general formula (BS-1).

In general formula (BS-1),
Each R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.

Although carbon number of the alkyl group as R is not specifically limited, Usually, it is 1-20, Preferably it is 1-12.
Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, it is 3-20, Preferably it is 5-15.
Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20, Preferably it is 7-11. Specific examples include a benzyl group.

In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.
In the compound represented by the general formula (BS-1), it is preferable that at least two of R are organic groups.

  Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexyl. Methylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

  Further, the basic compound represented by the general formula (BS-1) is preferably a basic compound in which at least one of the three Rs is an alkyl group having a hydrophilic group. And a good pattern shape can be formed.

  The alkyl group having a hydrophilic group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.

  Examples of the alkyl group having a hydrophilic group include an alkyl group having a hydroxy group or a mercapto group. Specific examples of such a basic compound having an alkyl group include triethanolamine and N, N-dihydroxyethylaniline.

Moreover, as an alkyl group which has said hydrophilic group, the alkyl group which has an oxygen atom, a sulfur atom, or a carbonyl group in an alkyl chain is also mentioned. That is, the alkyl group as R may be an oxyalkylene chain, a thioalkylene chain, or a ketoalkylene chain. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specifically, for example, tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.

  The alkyl group having the above hydrophilic group may be an alkyl group having a hydroxy group or a mercapto group as a substituent and having an oxygen atom, a sulfur atom or a carbonyl group in the alkyl chain.

  The alkyl group having the above hydrophilic group may further have a substituent, and examples of such a further substituent include a substituted or unsubstituted aryl group. When this aryl group is a substituted aryl group, examples of the substituent in the substituted aryl group include an alkyl group, an alkoxy group, and an aryl group.

(2) Compounds having a nitrogen-containing heterocyclic structure
This nitrogen-containing heterocycle may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Furthermore, you may contain hetero atoms other than nitrogen. Specifically, for example, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

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

(3) Amine compound having a phenoxy group
An amine compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.

This compound more preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is particularly preferable.

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and paragraph [0066] of US2007 / 0224539A1. ] Compounds (C1-1) to (C3-3) exemplified in the above.

  The amine compound having a phenoxy group is prepared by reacting, for example, a primary or secondary amine having a phenoxy group with a haloalkyl ether, and adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. And then extracted with an organic solvent such as ethyl acetate and chloroform. In addition, the amine compound having a phenoxy group reacts by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal, and a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can also be obtained by adding an aqueous solution and then extracting with an organic solvent such as ethyl acetate and chloroform.

(4) Ammonium salt
As the basic compound, an ammonium salt can also be used as appropriate.
Examples of the anion of the ammonium salt include halides, sulfonates, borates, and phosphates. Of these, halides and sulfonates are particularly preferred.

  As the halide, chloride, bromide and iodide are particularly preferable.

  As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.

  The alkyl group contained in the alkyl sulfonate may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.

  Examples of the aryl group contained in the aryl sulfonate include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent. As this substituent, a C1-C6 linear or branched alkyl group and a C3-C6 cycloalkyl group are preferable, for example. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferable. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The ammonium salt may be hydroxide or carboxylate. In this case, the ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.). It is particularly preferred.

  Preferred basic compounds include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholine. . These may further have a substituent. Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.

(5) A compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from proton acceptor property to acidity ( PA)
The composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. It may further contain a compound (hereinafter also referred to as compound (PA)) that generates a compound that has changed into an acidic state.

  The proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron. For example, a functional group having a macrocyclic structure such as a cyclic polyether or a π-conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

  Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.

  The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.

  Proton acceptor property can be confirmed by measuring pH.

  In the present invention, the acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1. And more preferably −13 <pKa <−3.

  In the present invention, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution. For example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.) It shows that acid strength is so large that this value is low. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett The values based on the substituent constants and the database of known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)
The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. The compound represented by the general formula (PA-1) has an acidic group as well as a proton acceptor functional group, so that the proton acceptor property is reduced or disappeared compared to the compound (PA), or from the proton acceptor property. It is a compound that has changed to acidic.

In general formula (PA-1),
Q _represents -SO 3 H, _-CO 2 H, or _-X 1 _NHX 2 _{R f.} Here, R _f represents an alkyl group, a cycloalkyl group, or an aryl group, and X ₁ and X ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or -N (Rx) Ry-. Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a divalent organic group. It may combine with Ry to form a ring, or may combine with R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

  Moreover, in this invention, compounds (PA) other than the compound which generate | occur | produces the compound represented by general formula (PA-1) can also be selected suitably. For example, an ionic compound that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

In the formula, A represents a sulfur atom or an iodine atom.
m represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.
R represents an aryl group.
R _N represents an aryl group substituted with a proton acceptor functional group.
X ⁻ represents a counter anion.

X ^- include specific examples of, X in formula (ZI) ^- it includes the same as.

Specific examples of the aryl group of R and R _N is a phenyl group are preferably exemplified.
Specific examples of the proton acceptor functional group R _N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).

  In the composition of the present invention, the compounding ratio of the compound (PA) in the whole composition is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass in the total solid content.

(6) Ionic compounds
The composition of the present invention can contain an ionic compound that becomes a weak acid relative to the acid generator. An onium salt is preferred as the ionic compound. When an acid generated from an acid generator upon irradiation with actinic rays or radiation collides with an onium salt having an unreacted weak acid anion, an onium salt having a strong acid anion is generated by releasing a weak acid by salt exchange. In this process, the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

  The onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (4), (5), and (6).

In general formula (4),
X ₄ ⁺ represents a cation.
Rz ₄ represents a cyclic group, an alkyl group or an alkenyl group.

In general formula (5),
X ₅ ⁺ represents a cation.
Rz ₅ represents a cyclic group, an alkyl group or an alkenyl group. However, it is assumed that no fluorine atom is bonded to the carbon atom adjacent to the S atom.

In general formula (6),
X ₆ ⁺ represents a cation.
Rz _6a and Rz _6b each independently represent a cyclic group, an alkyl group or an alkenyl group.
Z ₁ and Z ₂ each independently represents a single bond or a divalent linking group. However, the case where Z ₁ and Z ₂ are both —SO ₂ — is excluded.

Hereinafter, the general formula (4) will be described.
X ₄ ⁺ represents a cation.
Rz ₄ represents a cyclic group, an alkyl group or an alkenyl group. The cyclic group, alkyl group, and alkenyl group of Rz ₄ may each have a substituent.
Examples of the cation of X ₄ ⁺ include a sulfonium or iodonium cation. Preferable examples of the sulfonium cation or iodonium cation represented by X ₄ ⁺ include the sulfonium cation exemplified in General Formula (ZI).

Cyclic group Rz _4, for example, an aryl group and a cycloalkyl group. The cyclic group for Rz ₄ may be monocyclic or polycyclic. Examples of the substituent that the cyclic group of Rz ₄ may have include a hydroxyl group, an alkyl group, an alkoxy group, a halogen atom such as a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and A nitro group etc. are mentioned.

The alkyl group for Rz ₄ preferably has, for example, 1 to 30 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the substituent that the alkyl group of Rz ₄ may have include a hydroxyl group, an alkyl group, a halogen atom such as a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and a nitro group. Can be mentioned.

Examples of the alkenyl group for Rz ₄ include alkenyl groups having 2 to 10 carbon atoms, which may be linear or branched. The alkenyl group for Rz ₄ is preferably a linear alkenyl group having 2 to 4 carbon atoms. The linear alkenyl group having 2 to 4 carbon atoms is preferably a vinyl group or a propenyl group. Examples of the substituent that the alkenyl group of Rz ₄ may have include a halogen atom such as a hydroxyl group, an alkyl group, and a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and a nitro group. .

  Preferable examples of the anion moiety of the compound represented by the general formula (4) include the structures exemplified in paragraph [0198] of JP2012-242799A.

  Although the specific example of the anion part of the compound represented by General formula (4) below is shown, it is not limited to these.

The general formula (5) will be described below.
X ₅ ⁺ represents a cation.
Rz ₅ represents a cyclic group, an alkyl group or an alkenyl group. The cyclic group, alkyl group, and alkenyl group of Rz ₅ may each have a substituent. However, it is assumed that no fluorine atom is bonded to the carbon atom adjacent to the S atom.

Examples of the cation of X ₅ ⁺ include a sulfonium or iodonium cation. Preferable examples of the sulfonium cation or iodonium cation represented by X ₅ ⁺ include the sulfonium cation exemplified in general formula (ZI) and the iodonium cation exemplified in general formula (ZII).

Cyclic group Rz _5, for example, an aryl group and a cycloalkyl group. The cyclic group for Rz ₅ may be monocyclic or polycyclic. Examples of the substituent that the cyclic group of Rz ₅ may have include a halogen atom such as a hydroxyl group, an alkyl group, and a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and a nitro group. It is done.

Alkyl group Rz _5, for example, preferably from 1 to 30 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the substituent that the alkyl group of Rz ₅ may have include a halogen atom such as a hydroxyl group, an alkyl group, and a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and a nitro group. .

Examples of the alkenyl group for Rz ₅ include an alkenyl group having 2 to 10 carbon atoms, which may be linear or branched. The alkenyl group for Rz ₄ is preferably a linear alkenyl group having 2 to 4 carbon atoms. The linear alkenyl group having 2 to 4 carbon atoms is preferably a vinyl group or a propenyl group. Examples of the substituent that the alkenyl group of Rz ₅ may have include a hydroxyl group, an alkyl group, a halogen atom such as a fluorine atom, a halogenated alkyl group, a carbonyl group, an ether bond, an ester bond, and a nitro group. Can be mentioned.

  Preferable examples of the anion moiety of the compound represented by the general formula (5) include the structure exemplified in paragraph [0201] of JP2012-242799A.

  Although the specific example of the anion part of the compound represented by General formula (5) below is shown, it is not limited to these.

The general formula (6) will be described below.
X ₆ ⁺ represents a cation.
Rz _6a and Rz _6b each independently represent a cyclic group, an alkyl group or an alkenyl group. The cyclic group, alkyl group, and alkenyl group of Rz _6a and Rz _6b may each have a substituent.
Z ₁ and Z ₂ each independently represents a single bond or a divalent linking group. However, the case where Z ₁ and Z ₂ are both —SO ₂ — is excluded.

Preferable examples of the sulfonium cation or iodonium cation represented by X ₆ ⁺ include a sulfonium cation exemplified by the general formula (ZI) and an iodonium cation exemplified by the general formula (ZII).

Examples of the cyclic group of Rz _6a and Rz _6b include an aryl group and a cycloalkyl group. Cyclic groups Rz _6a and _{Rz 6b} can be a single ring, alkyl group of polycyclic, which may be a Rz _6a and _{Rz 6b,} for example, preferably from 1 to 30 carbon atoms, carbon atoms More preferably, it is 3-10.

Examples of the alkenyl group of Rz _6a and Rz _6b include an alkenyl group having 2 to 10 carbon atoms, and may be linear or branched. The alkenyl group for Rz ₄ is preferably a linear alkenyl group having 2 to 4 carbon atoms. The linear alkenyl group having 2 to 4 carbon atoms is preferably a vinyl group or a propenyl group.

The substituents that each of the cyclic group, alkyl group, and alkenyl group of Rz _6a and Rz _6b may have include, for example, a halogen atom such as a hydroxyl group, an alkyl group, and a fluorine atom, a halogenated alkyl group, a carbonyl group, and an ether. Examples include a bond, an ester bond, and a nitro group.

The divalent linking group of Z ₁ and Z ₂ is, for example, a divalent hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group) which may have a substituent, or a divalent containing a hetero atom. And the like. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group. The divalent linking group of Z ₁ and Z ₂ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is preferably a linear or branched alkylene group, and more preferably a methylene group or an ethylene group.

  Preferable examples of the anion moiety of the compound represented by the general formula (6) include structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.

  Although the specific example of the anion part of the compound represented by General formula (6) below is shown, it is not limited to these.

  Specific examples of the compounds represented by the general formulas (4) to (6) are shown below, but are not limited thereto.

  The onium salt that is a weak acid relative to the acid generator is a compound (C) having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety being linked by a covalent bond ( (Hereinafter also referred to as “compound (CA)”).

  The compound (CA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

In general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
-X ^- it ^is, -COO _^-, -SO 3 _- represents an anion portion selected from ^{_{-R 4 -, -SO 2 -,}} -N. R ₄ has 1 having a carbonyl group: —C (═O) —, a sulfonyl group: —S (═O) ₂ —, and a sulfinyl group: —S (═O) — at the site of connection with the adjacent N atom. Represents a valent substituent.
R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In (C-3), two of R _{1 to} R ₃ may be combined to form a double bond with the N atom.

Examples of the substituent having 1 or more carbon atoms in R _{1 to} R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino. A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.

L ₁ as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L ₁ is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

  Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.

  Preferable examples of the compound represented by the general formula (C-2) include the compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.

  Preferable examples of the compound represented by the general formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.

  In addition, as an acid diffusion controller (C) that can be used in the composition according to the present invention, compounds synthesized in Examples of JP-A No. 2002-363146, and paragraph 0108 of JP-A No. 2007-298869 And the compounds described.

  As the acid diffusion controller (C), a photosensitive basic compound may be used. As the photosensitive basic compound, for example, JP-T-2003-524799 and J. Org. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) etc. can be used.

  The molecular weight of the acid diffusion controller (C) is usually 100 to 1500, preferably 150 to 1300, and more preferably 200 to 1000.

  These acid diffusion control agents (C) may be used alone or in combination of two or more.

  When the composition according to the present invention contains the acid diffusion controller (C), the content is preferably 0.01 to 8.0% by mass based on the total solid content of the composition, More preferably, it is 0.1-5.0 mass%, and it is especially preferable that it is 0.2-4.0 mass%.

  The molar ratio of the acid diffusion controller (C) to the photoacid generator (B) is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, More preferably, it is 0.1-3.

[4] Hydrophobic resin (D)
The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”). The hydrophobic resin has at least one of a fluorine atom and a silicon atom. The hydrophobic resin (D) is different from the resin (A).
At least one of a fluorine atom and a silicon atom in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chain.

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

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

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

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

  Preferable examples of the hydrophobic resin (D) of the present invention include hydrophobic resins described in paragraphs [0299] to [0491] of JP 2012-093733 A.

  Since the composition of the present invention contains a hydrophobic resin containing at least one of fluorine atoms and silicon atoms, the hydrophobic resin is unevenly distributed in the surface layer of the film formed from the composition, and the immersion medium is water. In this case, the receding contact angle of the film surface with respect to water can be improved, and immersion water followability can be improved.

  After the coating film comprising the composition of the present invention is baked and before exposure, the receding contact angle of the film is preferably 60 ° to 90 ° at the temperature during exposure, usually room temperature 23 ± 3 ° C., humidity 45 ± 5%, More preferably, it is 65 ° or more, more preferably 70 ° or more, and particularly preferably 75 ° or more.

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

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

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

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

  When the hydrophobic resin has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the weight average molecular weight of the hydrophobic resin. Moreover, it is preferable that it is 10-90 mass% with respect to all the repeating units of hydrophobic resin, 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 hydrophobic resin is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 30,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: tetrahydrofuran (THF)).

Hydrophobic resins can be used alone or in combination of two or more.
The content of the hydrophobic resin in the composition can be appropriately adjusted and used so that the receding contact angle of the actinic ray-sensitive or radiation-sensitive resin film falls within the above range. The content is preferably 01 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 8% by mass.

[5] Solvent
The composition according to the present invention may further contain a solvent.
Typically, an organic solvent is used as this solvent. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and a ring. Good monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate are mentioned.

  Examples of alkylene glycol monoalkyl ether carboxylates include propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate. And propylene glycol monobutyl ether acetate, 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 Examples include glycol monomethyl ether and ethylene glycol monoethyl ether.

  Examples of the lactate alkyl ester include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

  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. And 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 and 3- And methylcycloheptanone.

  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.

  Examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

  As the solvent, it is preferable to use a solvent having a boiling point of 130 ° C. or higher under normal temperature and pressure. Specifically, for example, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, PGMEA, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid-2 -(2-Ethoxyethoxy) ethyl and propylene carbonate are mentioned.

  These solvents may be used alone or in combination of two or more. In the latter case, it is preferable to use a mixed solvent of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group.

  Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, PGME, propylene glycol monoethyl ether, and ethyl lactate. Of these, PGME and ethyl lactate are particularly preferred.

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

  When using a mixed solvent of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group, these mass ratios are preferably 1/99 to 99/1, more preferably 10/90 to 90/10, More preferably, it is set to 20/80 to 60/40.

  When a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is used, particularly excellent coating uniformity can be achieved. The solvent is particularly preferably a mixed solvent of PGMEA and one or more other solvents.

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

[6] Surfactant
The composition of the present invention 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-described surfactant, it is possible to provide a resist 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. It becomes.

  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), MegaFuck F171, F173, F176, F189, F113, F110, F177, F120, R08 (Dainippon Ink Chemical Co., Ltd.), 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 S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G230G 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

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

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

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 C ₃ F ₇ groups 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 any combination.
The content of the surfactant is preferably 0 to 2% by mass, more preferably 0 to 1.5% by mass, based on the total solid content (total amount excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. %, Particularly preferably 0 to 1% by mass.

[7] Carboxylic acid onium salt
The composition of the present invention may contain a carboxylic acid onium salt. As the carboxylic acid onium salt, an iodonium salt and a sulfonium salt are preferable. As the 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.

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

[8] Dissolution-inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid and increases the solubility in an alkaline developer.
The composition of the present invention may contain a dissolution-inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “dissolution-inhibiting compound”) that is decomposed by the action of an acid to increase the solubility in an alkaline developer. . The dissolution inhibiting compound contains an acid-decomposable group, such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724,355 (1996), in order not to lower the permeability of 220 nm or less. Preferred are alicyclic or aliphatic compounds. Examples of the acid-decomposable group and the alicyclic structure are the same as those described for the resin (A).

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

The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.
Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

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

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

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

<Pattern formation method>
The present invention relates to a pattern forming method using such an actinic ray-sensitive or radiation-sensitive resin composition, and the steps that can be included in the pattern forming method of the present invention are described below.

[Step (1): Application step]
The procedure of step (1) is not particularly limited, but a method of applying the composition of the present invention on a substrate and subjecting it to a curing treatment (coating method) if necessary, or actinic ray sensitivity on a temporary support. Alternatively, a method of forming a radiation-sensitive film and transferring the actinic ray-sensitive or radiation-sensitive film onto the substrate can be used. Of these, the coating method is preferable in terms of excellent productivity.

The substrate is not particularly limited, and is an inorganic substrate of silicon, SiN, SiO ₂ or TiN, a coating inorganic substrate such as SOG (Spin on Glass), a semiconductor manufacturing process such as an IC, a circuit substrate such as a liquid crystal or a thermal head. In addition, a substrate generally used in the lithography process of other photofabrication processes can be used. Furthermore, if necessary, an antireflection film may be formed between the resist film and the substrate. As the antireflection film, a known organic or inorganic antireflection film can be appropriately used. Further, the pattern forming method of the present invention may be combined with a two-layer resist process as disclosed in, for example, Japanese Patent Application Laid-Open No. 2008-083384, and exposure and exposure as disclosed in International Publication No. 2011/122336 pamphlet. It may be combined with a process having multiple developments. When combining the present invention and the process disclosed in WO 2011/122336 pamphlet, the pattern forming method of the present invention is used as the second negative pattern forming method in claim 1 of WO 2011/122336 pamphlet. It is preferable to apply.

(Actinic ray-sensitive or radiation-sensitive film)
The thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 1 to 500 nm, more preferably 1 to 100 nm, because a highly accurate fine pattern can be formed. . Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.

[Step (2): Exposure step]
Step (2) is a step of irradiating (exposing) actinic rays or radiation to the film (actinic ray-sensitive or radiation-sensitive film) formed in step (1).

  The light used for the exposure is not particularly limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Preferably, it is far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.

More specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, and the like can be mentioned. ArF excimer laser, EUV or electron beam is preferable, and ArF excimer laser is more preferable.

  In the exposure step, an immersion exposure method can be applied. The immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method. Immersion exposure can be performed, for example, according to the method described in paragraphs [0594] to [0601] of JP2013-242397A.

  In addition, when the receding contact angle of the actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is too small, it cannot be suitably used for exposure through an immersion medium, and The effect of reducing water residue (watermark) defects cannot be fully exhibited. In order to realize a preferable receding contact angle, it is preferable to include the hydrophobic resin (D) in the composition. Alternatively, an immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) formed of the hydrophobic resin (D) may be provided on the actinic ray-sensitive or radiation-sensitive film. A top coat may be provided on the actinic ray-sensitive or radiation-sensitive film containing the hydrophobic resin (D). The functions necessary for the top coat are suitability for application to the actinic ray-sensitive or radiation-sensitive film upper layer, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the composition film and can be uniformly applied to the upper layer of the composition film.

  The topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. For example, based on the description in paragraphs [0072] to [0082] of JP-A-2014-059543 Can be formed.

  It is preferable to form a top coat containing the basic compound described in JP2013-61648A on the resist film.

  Further, even when exposure is performed by a method other than the immersion exposure method, a top coat may be formed on the actinic ray-sensitive or radiation-sensitive film.

  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 the actinic ray-sensitive or radiation-sensitive film is important, and the ability to follow the high-speed scanning of the exposure head without remaining droplets is the actinic ray-sensitive or radiation-sensitive property. It is required for the resin composition.

  After the step (2), before the step (3) described later, a heat treatment (PEB: Post Exposure Bake) may be applied to the film irradiated with the actinic ray or radiation in the step (2). By this step, the reaction of the exposed part is promoted. The heat treatment (PEB) may be performed a plurality of times.

  The temperature of the heat treatment is preferably 70 to 130 ° C, and more preferably 80 to 120 ° C.

  The time for the heat treatment is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds.

  The heat treatment can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

[Step (3): Development step]
The pattern formation process of this invention has a image development process. The developer is not particularly limited, and examples include a developer containing an alkali developer and an organic solvent.

  Step (3) may be a step of developing the film irradiated with actinic rays or radiation in step (2) using an alkali developer.

  As the alkali developer, an alkali aqueous solution containing an alkali is preferably used. The type of the alkaline aqueous solution is not particularly limited. For example, an alkali containing a quaternary ammonium salt represented by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, a cyclic amine, or the like. An aqueous solution etc. are mentioned. Among these, an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH) is preferable. An appropriate amount of alcohol, surfactant or the like may be added to the alkaline developer. The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0.

  Step (3) is a step of developing the film irradiated with actinic rays or radiation in step (2) using a developer containing an organic solvent (hereinafter also referred to as “organic solvent developer”). May be. Development is preferably performed using a developer containing an organic solvent in that the top coat can be peeled off and developed at the same time.

  As the organic solvent developer, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

  Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, 2- Examples thereof include methyl hydroxyisobutyrate, isobutyl isobutyrate, butyl propionate, butyl butanoate and isoamyl acetate.

  Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, alcohols such as n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, methoxymethylbutanol It can be mentioned glycol ether solvents or the like.

  Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.

  Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

  Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

  A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.

  That is, the amount of the organic solvent used relative to the organic solvent developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.

  In particular, the organic solvent developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

  The vapor pressure of the organic solvent developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic solvent developer to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.

  An appropriate amount of a surfactant can be added to the organic solvent developer as required.

  The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

  The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

  The organic solvent developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the organic solvent developer used in the present invention are the same as those in the basic compound that can be contained in the composition described above as the acid diffusion controller.

  As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain time (dip method), a method in which a developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied. The preferred range of the discharge pressure of the discharged developer and the method for adjusting the discharge pressure of the developer are not particularly limited. For example, paragraphs [0631] to [0631] to [ 0636] can be used.

  In one aspect of the pattern forming method of the present invention, a step of developing using an organic solvent developer (organic solvent developing step) and a step of developing using an aqueous alkali solution (alkali developing step) are used in combination. May be. Thereby, a finer pattern can be formed.

  As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.

  In the present invention, a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 [0077]. ] And the same mechanism).

  In one aspect of the pattern forming method of the present invention, the order of the alkali development step and the organic solvent development step is not particularly limited, but it is more preferable to perform the alkali development before the organic solvent development step.

  It is preferable to include the process of wash | cleaning using a rinse liquid after the process developed using the developing solution containing an organic solvent.

  The rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. . As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents should be used. Is preferred.

  Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.

  More preferably, after the step of developing using a developer containing an organic solvent, at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and hydrocarbon solvents. A step of washing with a rinsing liquid containing an organic solvent is performed, more preferably a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent, and particularly preferably a monohydric alcohol is contained. The washing step is performed using a rinse solution, and most preferably, the washing step is performed using a rinse solution containing a monohydric alcohol having 5 or more carbon atoms.

  The rinsing liquid containing a hydrocarbon solvent is preferably a hydrocarbon compound having 6 to 30 carbon atoms, more preferably a hydrocarbon compound having 8 to 30 carbon atoms, and particularly preferably a hydrocarbon compound having 10 to 30 carbon atoms. Especially, pattern collapse is suppressed by using the rinse liquid containing a decane and / or undecane.

  When an ester solvent is used as the organic solvent, a glycol ether solvent may be used in addition to the ester solvent (one or more). Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) as a subcomponent. Thereby, a residue defect is suppressed more.

  Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl- 2-pentanol (methyl isobutyl carbinol: MIBC), 1-pentanol, - or the like can be used methyl-1-butanol.

  A plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.

  The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

  The vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution.

  In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

   Various materials used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention (for example, a resist solvent, a developer, a rinse solution, an antireflection film-forming composition, a top The coating forming composition or the like) preferably does not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 10 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less.

  Examples of a method for removing impurities such as metals from the various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be a composite material obtained by combining these materials and ion exchange media. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.

  Further, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. For example, the inside of the apparatus may be lined with Teflon (registered trademark), and distillation may be performed under a condition in which contamination is suppressed as much as possible. The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.

In addition to filter filtration, impurities may be removed by an adsorbent, or filter filtration and adsorbent may be used in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent metal impurities from being mixed in the manufacturing process. Whether or not the metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing apparatus. The content of the metal component contained in the cleaning liquid after use is more preferably 100 ppt (parts per trigger) or less, further preferably 10 ppt or less, and particularly preferably 1 ppt or less.

  Organic processing liquids such as developers and rinse liquids contain conductive compounds to prevent chemical piping and various parts (filters, O-rings, tubes, etc.) from being damaged due to electrostatic charging and subsequent electrostatic discharge. It may be added. Although it does not restrict | limit especially as an electroconductive compound, For example, methanol is mentioned. The addition amount is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics and rinse characteristics. Regarding chemical solution piping members, SUS (stainless steel) or various pipes coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can. Similarly, polyethylene, polypropylene, or fluorine resin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.

  A method for improving the surface roughness of the pattern may be applied to the pattern formed by the method of the present invention. As a method for improving the surface roughness of the pattern, for example, a method of treating a resist pattern with a plasma of a hydrogen-containing gas disclosed in International Publication No. 2014/002808 can be mentioned. In addition, JP 2004-235468 A, US Patent Application Publication No. 2010/0020297, JP 2008-83384 A, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.

  The pattern forming method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823).

  Further, the resist pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.

  The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.

  The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA (Office Automation) / media related equipment, optical equipment, communication equipment, etc.).

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not limited by this.

<Resin (A)>
[Synthesis Example 1: Synthesis of Resin (P-1)]
Monomers 1, 2 and 3 shown below were prepared at a ratio (molar ratio) of 20/60/20. These were dissolved in cyclohexanone to prepare 450 g of a solution having a solid concentration of 15% by mass. To this solution, 0.8 mol% of Wako Pure Chemicals polymerization initiator V-601 was added and added dropwise to 50 g of cyclohexanone heated to 100 ° C. in a nitrogen atmosphere over 6 hours. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature and crystallized in 5 L of methanol. The precipitated white powder was collected by filtration to recover the target resin P-1.

About the obtained resin (P-1), by GPC (carrier: tetrahydrofuran (THF)) measurement, a weight average molecular weight (Mw: polystyrene conversion), a number average molecular weight (Mn: polystyrene conversion), and dispersity (Mw / Mn) Was calculated. In addition, the composition ratio (molar ratio) was calculated by ¹ H-NMR (Nuclear Magnetic Resonance) and ¹³ C-NMR measurement.

The weight average molecular weight of the obtained resin (P-1) was 13500, the dispersity (Mw / Mn) was 1.48, and the composition ratio measured by ¹³ C-NMR was 20/60/20. It was.

[Synthesis Example 2: Resins (P-2) to (P-17)]
Resins (P-2) to (P-17) were synthesized by the same method as for resin (P-1). Moreover, resin (RP-1)-(RP-7) was used as resin for a comparison.

  The structure of the synthesized comparative resin is shown below together with the composition ratio (molar ratio) of repeating units, mass average molecular weight (Mw), and dispersity (Mw / Mn).

<Photoacid generator (B)>
The following compounds (A-1) to (A-4), compounds (RA-1) and (RA-2) were prepared as the photoacid generator (B).

<Acid diffusion controller (C)>
The following compounds (RB-1) and (B-2) to (B-6) were prepared as the acid diffusion controller (C).

<Hydrophobic resin (D)>
The following (N-1) to (N-12) were prepared as the hydrophobic resin (D). Hereinafter, the synthesis example of resin (N-1) is shown as an example.

[Synthesis Example 3: Hydrophobic resin (N-1)]
First, a monomer corresponding to each repeating unit of the resin (N-1) was prepared at a ratio (molar ratio) of 40/20/40. These were dissolved in PGMEA to prepare 450 g of a solution having a solid concentration of 15% by mass. To this solution, 0.6 mol% of Wako Pure Chemical Co., Ltd. polymerization initiator V-601 was added, and this was added dropwise to 50 g of PGMEA heated to 100 ° C. in a nitrogen atmosphere over 6 hours. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature and crystallized in 5 L of methanol. The precipitated white powder was collected by filtration to recover the target resin (N-1).

The obtained hydrophobic resin (N-1) has a weight average molecular weight of 20000, a dispersity (Mw / Mn) of 1.4, and a composition ratio measured by ¹³ C-NMR of 40/20/40. there were. The weight average molecular weight, the degree of dispersion, and the composition ratio were determined in the same manner as for the resin (A).

  Hydrophobic resins (N-2) to (N-12) were also synthesized by the same method.

  Table 1 below summarizes the composition ratio (molar ratio), mass average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit of the synthesized resin. The synthesized resin is shown below.

<Solvent>
The following were prepared as solvents.
SL-1: Propylene Glycol Monomethyl Ether Acetate (PGMEA)
SL-2: Propylene Glycol Monomethyl Ether (PGME)
SL-3: cyclohexanone SL-4: γ-butyrolactone SL-5: propion carbonate <surfactant>
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd .; fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd .; fluorine and silicon)
W-3: Troisol S-366 (manufactured by Troy Chemical Co .; fluorine type)
W-4: PF656 (manufactured by OMNOVA; fluorine-based)
W-5: PF6320 (manufactured by OMNOVA; fluorine-based)
<Preparation of resist composition>
The components shown in the following Tables 2 to 4 are dissolved in the solvents shown in the following Tables 2 to 4, and the solutions having the solid content concentrations shown in the following Tables 2 to 4 are prepared, and further, polyethylene filters having a pore size of 0.03 μm. Then, a resist composition was prepared by filtration.

<Examples 1-1 to 1-31 and Comparative Examples 1-1 to 1-20: ArF immersion exposure>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. The prepared resist composition was applied on the formed antireflection film, and baked at 130 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. The formed resist film was exposed through a 6% halftone mask of 1: 1 line and space pattern having a line width of 48 nm using an ArF excimer laser immersion scanner (XT1700i, NA1.2 manufactured by ASML). Ultra pure water was used as the immersion liquid. Then, after heating at 130 ° C. for 60 seconds, the film was developed with an aqueous tetramethylammonium hydroxide solution (2.38% by mass) or an alkaline solution for 30 seconds, rinsed with pure water, and then spin-dried to form a pattern.

[Evaluation of LWR (Line Width Roughness)]
The obtained line / space = 1/1 line pattern (ArF line width 48 nm, EB / EUV line width 100 nm) was observed with a scanning microscope (S9380 manufactured by Hitachi, Ltd.), and the edge of the line pattern in the longitudinal direction was 2 μm. The line width was measured at 50 points, the standard deviation was determined for the measurement variation, and 3σ was calculated. A smaller value indicates better performance. The results are shown in Table 5 below. The unit of the evaluation result is nm.

[Evaluation of coating defects]
The resist composition was applied onto a silicon wafer by a spin coater and baked at 130 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. The number of coating defects was measured with a KLA 2360 machine (manufactured by KLA Tencor). At this time, the number of defects in Comparative Example 1-1 was normalized to 1 and represented. A smaller value indicates better coating defect performance. The results are shown in Table 5 below.

[Evaluation of Contact Angle (CA)]
The prepared resist composition was applied onto a silicon wafer and baked at 130 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. The contact angle of water droplets was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The droplet size was 35 μL. The measurement environment was 23 ± 3 ° C. and relative humidity 45 ± 5%. The results are shown in Table 5 below. The unit of the evaluation result is °.

<Example 2-1 and Comparative Examples 2-1 to 2-3: EB exposure>
The prepared actinic ray-sensitive or radiation-sensitive resin composition was applied on a 6-inch silicon wafer subjected to hexamethyldisilazane (HMDS) treatment using a spin coater Mark8 manufactured by Tokyo Electron, and hot at 120 ° C. for 60 seconds. It dried on the plate and the resist film with a film thickness of 0.05 micrometer was obtained. Pattern irradiation was performed using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). At this time, the drawing was performed so that the electron beam drawing portion having a width of 100 nm and the non-drawing portion were repeated. After irradiation, it was heated on a hot plate at 140 ° C. for 90 seconds. After developing with a developer (butyl acetate) for 30 seconds, the wafer was further rinsed with a rinse solution (methyl isobutyl carbinol (MIBC)) at 1500 rpm (rpm) for 30 seconds. Thereafter, it was rotated at a high speed of 2000 rpm (rpm) for 20 seconds and dried to obtain a pattern.

  About the obtained pattern, LWR and the coating defect were evaluated by the method similar to the above-mentioned. The results are shown in Table 6.

<Example 3-1 and Comparative Examples 3-1 to 3-3: EUV exposure>
The prepared actinic ray-sensitive or radiation-sensitive resin composition was applied on a 6-inch silicon wafer subjected to hexamethyldisilazane (HMDS) treatment using a spin coater Mark8 manufactured by Tokyo Electron, and hot at 120 ° C. for 60 seconds. It dried on the plate and the resist film with a film thickness of 0.05 micrometer was obtained. Pattern exposure was performed using EUV light (SEMATECH ALBANY, wavelength 13.5 nm). After irradiation, it was heated on a hot plate at 100 ° C. for 90 seconds. After developing with a developer (butyl acetate) for 5 seconds, the wafer was further rinsed with a rinse solution (methyl isobutyl carbinol (MIBC)) at 1500 rotations (rpm) for 30 seconds. Thereafter, it was rotated at a high speed of 2000 rpm (rpm) for 20 seconds and dried to obtain a pattern.

  About the obtained pattern, LWR and the coating defect were evaluated by the method similar to the above-mentioned. The results are shown in Table 7.

Claims (14)

(A) a resin containing a repeating unit (a) having at least two lactone structures, and
(B) A compound that generates an acid upon irradiation with actinic rays or radiation, and the fluorine atom content of the compound is 0 or more and 0.20 or less with respect to the total mass of all atoms contained in the compound. An actinic ray-sensitive or radiation-sensitive resin composition containing a compound. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a) having at least two lactone structures is a repeating unit represented by the following general formula (1).
In general formula (1),
Ra represents a hydrogen atom or an alkyl group.
Rb represents a partial structure having two or more lactone structures. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the compound (B) is a compound represented by the following general formula (2).
In general formula (2),
X ₁ and X ₂ each independently represents a fluorine atom or a fluoroalkyl group.
L represents a divalent linking group. When m ≧ 2, each L may be the same or different.
m represents an integer of 0 or more.
Y represents a divalent linking group.
R ₁ represents a hydrogen atom, an alkyl group or a group having a cyclic structure.
M ₁ ⁺ represents a cation. The resin (A) further contains a repeating unit (b) having an acid-decomposable group, and the repeating unit (b) is a repeating unit represented by the following general formula (3). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.
In general formula (3),
R ₁ represents a hydrogen atom or an alkyl group.
Rd _{1 to} Rd ₃ each independently represents a hydrogen atom or an alkyl group.
Z represents a monocyclic structure. Furthermore,
(C1) a basic compound having a hydrophilic functional group, or
(C2) The actinic ray-sensitive or sensation according to any one of claims 1 to 4, which contains at least one ionic compound represented by the following general formulas (4), (5) and (6). Radiation resin composition.
In general formula (4),
X ₄ ⁺ represents a cation.
Rz ₄ represents a cyclic group, an alkyl group or an alkenyl group.
In general formula (5),
X ₅ ⁺ represents a cation.
Rz ₅ represents a cyclic group, an alkyl group or an alkenyl group. However, it is assumed that no fluorine atom is bonded to the carbon atom adjacent to the S atom.
In general formula (6),
X ₆ ⁺ represents a cation.
Rz _6a and Rz _6b each independently represent a cyclic group, an alkyl group or an alkenyl group.
Z ₁ and Z ₂ each independently represents a single bond or a divalent linking group. However, the case where Z ₁ and Z ₂ are both —SO ₂ — is excluded.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, further comprising (D) a hydrophobic resin containing at least one of a fluorine atom and a silicon atom.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a) is a repeating unit having a structure in which at least two lactone structures are condensed. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (7).
In general formula (7),
Ra represents a hydrogen atom or an alkyl group.
Re _{1 to} Re ₈ each independently represents a hydrogen atom or an alkyl group.
Me ₁ represents a single bond or a divalent linking group.
Me ₂ and Me ₃ each independently represent a divalent linking group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 2 to 6, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (8). object.
In general formula (8),
Ra represents a hydrogen atom or an alkyl group.
M ₁ and M ₂ each independently represents a single bond or a linking group.
Lc ₁ and Lc ₂ each independently represent a group having a lactone structure. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 9, wherein the repeating unit represented by the general formula (8) is a repeating unit represented by the following general formula (9).
In general formula (9),
Ra represents a hydrogen atom or an alkyl group.
Mf ₁ and Mf ₂ each independently represents a single bond or a linking group.
Rf ₁ , Rf ₂ and Rf ₃ each independently represents a hydrogen atom or an alkyl group.
Mf ₁ and Rf ₁ may be bonded to each other to form a ring. Mf ₂ and Rf ₂ or Rf ₃ may be bonded to each other to form a ring. Applying the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10 on a substrate to form an actinic ray-sensitive or radiation-sensitive film;
A step of exposing the formed film, and
A pattern forming method including a step of developing the exposed film with a developer.   The pattern forming method according to claim 11, wherein the developer is a developer containing an organic solvent.   The manufacturing method of an electronic device containing the pattern formation method of Claim 11 or 12.   An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10.