JP2018155788A - Active ray- or radiation-sensitive resin composition, resist film, pattern formation metho, and electronic device production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an active ray- or radiation-sensitive resin composition capable of providing a pattern excellent in LWR performance; and a resist film, a pattern formation method and an electronic device production method that use the active ray- or radiation-sensitive resin composition.SOLUTION: The active ray- or radiation-sensitive resin composition comprises a resin having a repeating unit having a group represented by the general formula (1) in the figure.SELECTED DRAWING: None

Description

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

Conventionally, in the manufacturing process of a semiconductor device such as an IC (Integrated Circuit) and an LSI (Large Scale Integrated circuit), a fine pattern by lithography using an actinic ray-sensitive or radiation-sensitive resin composition is used. Processing is in progress.
For example, Patent Document 1 discloses a pattern forming method using a resin having a predetermined repeating unit.

International Publication No. 2016/052313

  When the present inventors examined the actinic-ray-sensitive or radiation-sensitive resin composition specifically described in the Example column of patent document 1, it formed with the said actinic-light-sensitive or radiation-sensitive resin composition. It was found that there is room for improvement with respect to the pattern width fluctuation (LWR (line width roughness)).

This invention makes it a subject to provide the actinic-ray-sensitive or radiation-sensitive resin composition which can obtain the pattern which is excellent in LWR performance.
Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.

As a result of intensive studies to achieve the above problems, the present inventors have found that the above problems can be solved by using a resin having a repeating unit having an acid-decomposable group having a specific structure, and have completed the present invention. .
That is, it has been found that the above problem can be solved by the following configuration.

(1) An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit having a group represented by the general formula (1) described later.
(2) The actinic ray-sensitive or radiation-sensitive resin composition according to (1), wherein the repeating unit is a repeating unit represented by the general formula (2) described later.
(3) The actinic ray-sensitive or radiation-sensitive resin composition according to (2), wherein X in the general formula (2) described later is a single bond.
(4) The actinic ray-sensitive material according to any one of (1) to (3) above, wherein Z in the general formula (1) described later is a group that forms a monocyclic alicyclic structure together with a carbon atom. Radiation sensitive resin composition.
(5) The actinic ray-sensitive or radiation-sensitive resin composition according to (4), wherein the alicyclic structure is an alicyclic structure having 5 or 6 carbon atoms.
(6) The actinic ray-sensitive or radiation-sensitive property according to any one of the above (1) to (5), wherein R ₁ in the general formula (1) described later is a chain alkyl group having 3 or more carbon atoms. Resin composition.
(7) The sensation according to any one of (1) to (5), wherein R ₁ and R ₂ in the general formula (1) to be described later are each independently a chain alkyl group having 2 or more carbon atoms. Actinic ray-sensitive or radiation-sensitive resin composition.
(8) A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (7) above.
(9) A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (7) above,
An exposure step of exposing the resist film;
A patterning method comprising: developing the exposed resist film with a developer.
(10) An electronic device manufacturing method including the pattern forming method according to (9).

ADVANTAGE OF THE INVENTION According to this invention, the actinic-ray-sensitive or radiation-sensitive resin composition which can obtain the pattern which is excellent in LWR performance can be provided.
Moreover, according to this invention, the resist film using the said actinic-ray-sensitive or radiation-sensitive resin composition, the pattern formation method, and the manufacturing method of an electronic device can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
About the description of group (atomic group) in this specification, the description which has not described substitution and non-substitution includes the group which has a substituent with the group which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the “organic group” refers to a group containing at least one carbon atom.
In the present specification, the term “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, deep ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-ray, and electron beam (EB). : Electron Beam) or the like. In the present specification, “light” means actinic rays or radiation.
Unless otherwise specified, “exposure” in the present specification includes not only exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, EUV light, etc., but also electron beams, and This includes drawing with particle beams such as ion beams.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In the present specification, (meth) acrylate represents acrylate and methacrylate.
In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of the resin are GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation). GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refractive index It is defined as a polystyrene-converted value by a detector (Refractive Index Detector).

[Actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also simply referred to as “composition” or “composition of the present invention”) will be described.
The composition of the present invention is a so-called resist composition, which may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development.
The composition of the present invention is typically a chemically amplified resist composition.

The characteristic point of the composition of the present invention includes a point including a resin having a repeating unit having a group represented by the general formula (1) described later. According to the composition of the present invention containing a predetermined resin, a pattern with particularly small fluctuation (LWR) in the pattern line width can be formed.
The details of this mechanism are not clear, but are presumed as follows. First, the total number of carbon atoms contained in R ₁ , R ₂ and R ₃ bonded to the carbon atom in the group represented by the general formula (1) is not less than a predetermined value. Therefore, the structure represented by —CR ₁ R ₂ R ₃ bonded to the carbon atom bonded to the oxygen atom in the general formula (1) is a bulky structure. As a result, the action of the acid tends to cause decomposition between the oxygen atom and the carbon atom. Therefore, the resist film made of the composition of the present invention has high photosensitivity and radiation sensitivity, and exhibits excellent development contrast. Therefore, it is considered that fluctuation of the pattern line width can be reduced.
In the present specification, “excellent LWR” means that the fluctuation of the pattern line width of a pattern formed by exposing and developing a resist film obtained from the composition is small.

  Hereinafter, the components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention will be described in detail.

<Resin (A)>
The composition of this invention contains resin which has a repeating unit which has group represented by General formula (1). The group represented by the general formula (1) functions as an acid-decomposable group that is decomposed by the action of an acid. In the formula, * represents a bonding position.

In general formula (1), R ₁ , R ₂ and R ₃ each independently represents a chain alkyl group. Here, the total number of carbon atoms contained in R ₁ , R ₂ and R ₃ is 5 or more.
The total number of carbon atoms contained in R ₁ , R ₂ and R ₃ is 5 or more means that the total number of carbon atoms contained in R ₁ , the number of carbon atoms contained in R ₂ , and the number of carbon atoms contained in R ₃ is 5 It is intended to be above.
The total number of carbon atoms may be 5 or more, usually 5 to 14 in many cases, and more often 5 to 10 in many cases. Among them, in terms of LWR more _excellent, the total number of carbon atoms contained in R 1, _{R 2} and _{R 3,} preferably 5-7, 5-6 is more preferable.
The chain alkyl group may be linear or branched.
The number of carbon atoms contained in the chain alkyl group is not particularly limited as long as the above total is within a predetermined range, but is usually 1 to 10 in many cases and more in 1 to 5 cases.
Among them, in terms of LWR more excellent, it is preferable number of carbon atoms in R ₁ is 3 or more. When R ₁ has 3 or more carbon atoms, R ₂ and R ₃ may each have 1 or more carbon atoms, and 1 to 3 are preferable and 1 to 2 are more preferable in that LWR is more excellent.
Moreover, it is also preferable that both R ₁ and R ₂ have 2 or more carbon atoms from the viewpoint that LWR is more excellent. When both R ₁ and R ₂ have 2 or more carbon atoms, the carbon number of R ₃ may be 1 or more, and 1 to 3 are preferable and 1 to 2 are more preferable in that LWR is more excellent.
In addition, when R ₁ , R ₂ and R ₃ have a substituent, the carbon number in the substituent is not included in the above total.

Z represents a group that forms a monocyclic or polycyclic ring structure with a carbon atom.
Examples of the cyclic structure formed by Z together with the carbon atom include a monocyclic structure and a polycyclic structure. The cyclic structure may contain a hetero atom. Moreover, the cyclic structure may or may not show aromaticity. Moreover, the said cyclic structure may have a substituent.
The cyclic structure is preferably an alicyclic structure in that the LWR is more excellent. That is, Z is preferably a group that forms a monocyclic or polycyclic alicyclic structure together with a carbon atom.
The number of carbon atoms contained in the monocyclic alicyclic structure is not particularly limited, but 4 to 10 is preferable, 4 to 7 is more preferable, and 5 or 6 is still more preferable in terms of more excellent LWR.
The number of carbon atoms contained in the polycyclic alicyclic structure is not particularly limited, but 7 to 20 is preferable and 7 to 15 is more preferable because LWR is more excellent. The polycyclic alicyclic structure is preferably a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group.

Especially, it is preferable that Z represents the group which forms a monocyclic alicyclic structure with a carbon atom at the point which LWR is more excellent. That is, it is preferable that the part represented by Z is an alkylene group (C3-C9 is preferable, C3-C6 is more preferable, and C4-C5 is still more preferable).
The preferred range of the number of carbon atoms contained in the monocyclic alicyclic structure is as described above.

The group represented by the general formula (1) may be bonded to the main chain in the resin via a linking group.
Especially, as a repeating unit which has group represented by General formula (1), the repeating unit represented by following General formula (2) is preferable at the point which LWR is more excellent.

In the general formula (2), the definitions of R ₁ , R ₂ , R ₃ and Z are the same as those in the general formula (1).

  In general formula (2), R represents a hydrogen atom, a halogen atom, or an organic group. As the organic group, an alkyl group is preferable, and a methyl group is more preferable.

In general formula (2), X represents a single bond or a divalent linking group. Examples of the divalent linking group include —COO — (— C (═O) —O—), —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, —SO—. , —SO ₂ —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group, and these Examples include groups in which a plurality are combined. Among these, an arylene group, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group- or -NHCO-alkylene group- are preferable.
When X is a divalent linking group, X is preferably —COOCH ₂ —.

  X is more preferably a single bond in that the LWR is more excellent. In other words, the resin (A) preferably has a repeating unit represented by the following general formula (2 ′).

  The method for synthesizing the resin having the repeating unit represented by the general formula (2) and / or the general formula (2 ′) is not particularly limited, and can be synthesized by polymerizing a monomer having the structure.

  Resin (A) may have the repeating unit which has group represented by General formula (1) individually by 1 type, and may have 2 or more types together.

  The content of the repeating unit having the group represented by the general formula (1) in the resin (A) is not particularly limited, but is 10% with respect to all the repeating units in the resin (A) because LWR is more excellent. -90 mol% is preferable, 20-80 mol% is more preferable, 30-70 mol% is still more preferable, 40-60 mol% is especially preferable.

  Although the specific example of the monomer corresponding to the repeating unit which has group represented by General formula (1) below is given, this invention is not limited to these specific examples.

The resin (A) may have another repeating unit other than the repeating unit having the group represented by the general formula (1).
For example, the resin (A) may have a repeating unit having an acid-decomposable group other than the repeating unit having the group represented by the general formula (1).

  The resin (A) also preferably has a repeating unit described in paragraphs [0336] to [0369] of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having another acid-decomposable group.

  Specific examples of the monomer corresponding to the repeating unit having another acid-decomposable group are shown below, but the present invention is not limited to these specific examples.

  Resin (A) may have the repeating unit which has an acid-decomposable group individually by 1 type, and may have 2 or more types together.

  The resin (A) preferably has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

The lactone structure or sultone structure may have a lactone structure or sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable. Among them, a 5- to 7-membered ring lactone structure in which another ring structure is condensed in a form forming a bicyclo structure or a spiro structure, or a 5- to 7-membered ring in a form forming a bicyclo structure or a spiro structure Those having other ring structures condensed to the sultone structure are more preferable.
The resin (A) is a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21), or any one of the following general formulas (SL1-1) to (SL1-3). It is more preferable to have a repeating unit having a sultone structure. A lactone structure or a sultone structure may be directly bonded to the main chain. As a preferable structure, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1 -21) or a sultone structure represented by the general formula (SL1-1).

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). As the substituent (Rb ₂ ), an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, A halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group is preferable, and an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group is more preferable. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. A plurality of substituents (Rb ₂ ) may be bonded to form a ring.

  As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III) is preferable.

In the general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
n is the number of repetitions of the structure represented by —R ₀ —Z—, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R ₀ -Z- does not exist and becomes a single bond.
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. If R ₀ is plural, R ₀ each independently represents a alkylene group, a cycloalkylene group, or a combination thereof.
Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are a plurality of Z, each Z independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
R ₇ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

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

The resin (A) may have a repeating unit having a carbonate structure. As the carbonate structure, a cyclic carbonate structure is preferable.
The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

In General Formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
n represents an integer of 0 or more.
R _A ² represents a substituent. When n is 2 or more, each R _A ² independently represents a substituent.
A represents a single bond or a divalent linking group.
Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with a group represented by —O—C (═O) —O— in the formula.

  The resin (A) is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure. Paragraphs [0370] to [0414] of US Patent Application Publication No. 2016 / 0070167A1 It is also preferable to have the repeating unit described in 1.

  Resin (A) may have one or more repeating units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, and may have two or more in combination. It may be.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and specific examples of the monomer corresponding to the repeating unit represented by the general formula (A-1) will be given below. It is not limited to these specific examples. The following specific examples correspond to the case where R ₇ in the general formula (III) and R _A ¹ in the general formula (A-1) are methyl groups, but R ₇ and R _A ¹ are a hydrogen atom or a halogen atom. Or can be optionally substituted with a monovalent organic group.

  In addition to the above monomers, the following monomers are also suitably used as the raw material for the resin (A).

  The content of a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure contained in the resin (A) (selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure) 5 to 70 mol% is preferable with respect to all repeating units in the resin (A), more preferably 10 to 65 mol%, and more preferably 20 to 20 mol% of the total number of repeating units having at least one kind. 60 mol% is more preferable.

The resin (A) may have a repeating unit having a polar group.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a fluorinated alcohol group.
The repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Moreover, it is preferable that the repeating unit which has a polar group does not have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornane group.

  Specific examples of the monomer corresponding to the repeating unit having a polar group are given below, but the present invention is not limited to these specific examples.

Other specific examples of the repeating unit having a polar group include the repeating units disclosed in paragraphs [0415] to [0433] of US Patent Application Publication No. 2016 / 0070167A1.
Resin (A) may have the repeating unit which has a polar group individually by 1 type, and may have 2 or more types together.
5-40 mol% is preferable with respect to all the repeating units in resin (A), content of the repeating unit which has a polar group has more preferable 5-30 mol%, and 10-25 mol% is still more preferable.

  The resin (A) may further have a repeating unit having neither an acid-decomposable group nor a polar group. The repeating unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure. Examples of the repeating unit having neither an acid-decomposable group nor a polar group include the repeating units described in paragraphs [0236] to [0237] of US Patent Application Publication No. 2016 / 0026083A1. Preferred examples of the monomer corresponding to the repeating unit having neither an acid-decomposable group nor a polar group are shown below.

Other specific examples of the repeating unit having neither an acid-decomposable group nor a polar group include the repeating unit disclosed in paragraph [0433] of US Patent Application Publication No. 2016 / 0070167A1. .
The resin (A) may have one type of repeating unit that has neither an acid-decomposable group nor a polar group, or may have two or more types in combination.
The content of the repeating unit having neither an acid-decomposable group nor a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, based on all repeating units in the resin (A). 5-25 mol% is still more preferable.

Resin (A) is, other than the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or further, general required characteristics of resist, resolving power, heat resistance, sensitivity, etc. Various repeating structural units may be included for the purpose of adjusting the above.
Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a predetermined monomer.

The predetermined monomer has one addition polymerizable unsaturated bond selected from, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Compounds and the like.
In addition, addition polymerizable unsaturated compounds that can be copolymerized with monomers corresponding to the above various repeating structural units may be used.
In the resin (A), the content molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.

  When the composition of the present invention is for ArF exposure, the resin (A) preferably has substantially no aromatic group from the viewpoint of ArF light transmittance. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less with respect to all repeating units in the resin (A). More preferably, 0 mol%, that is, it does not have a repeating unit having an aromatic group. The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

  In the resin (A), it is preferable that 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, it is preferable that the acrylate-based repeating unit is 50 mol% or less with respect to all repeating units of the resin (A).

When the composition of the present invention is for KrF exposure, EB exposure, or EUV exposure, the resin (A) preferably has a repeating unit having an aromatic hydrocarbon group. It is more preferable that the resin (A) has a repeating unit containing a phenolic hydroxyl group. Examples of the repeating unit containing a phenolic hydroxyl group include a hydroxystyrene repeating unit or a hydroxystyrene (meth) acrylate repeating unit.
When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (A) is a group (leaving group) in which the hydrogen atom of the phenolic hydroxyl group is decomposed and eliminated by the action of an acid. Preferably it has a protected structure.
The content of the repeating unit having an aromatic hydrocarbon group contained in the resin (A) is preferably from 30 to 100 mol%, more preferably from 40 to 100 mol%, based on all repeating units in the resin (A). 50 to 100 mol% is more preferable.

  The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, and 3,000 to 11,000. Particularly preferred. The dispersity (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further 1.1 to 2.0. preferable.

Resin (A) may be used individually by 1 type, and may use 2 or more types together.
The content of the resin (A) in the total solid content of the composition of the present invention is generally often 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and 80% by mass. The above is more preferable. Although an upper limit in particular is not restrict | limited, 99.5 mass% or less is preferable, 99 mass% or less is more preferable, and 97 mass% or less is still more preferable.

<Resin (B)>
When the composition of the present invention contains a crosslinking agent (G) described later, the composition of the present invention may contain an alkali-soluble resin (B) having a phenolic hydroxyl group (hereinafter also referred to as “resin (B)”). preferable. The resin (B) preferably has a repeating unit having a phenolic hydroxyl group.
In this case, typically, a negative pattern is suitably formed.
The crosslinking agent (G) may be supported on the resin (B).
The resin (B) may have the acid-decomposable group described above.

  The repeating unit having a phenolic hydroxyl group contained in the resin (B) is preferably a repeating unit represented by the following general formula (II).

In general formula (II),
R ₂ represents a hydrogen atom, an alkyl group (preferably a methyl group), or a halogen atom (preferably a fluorine atom).
B ′ represents a single bond or a divalent linking group.
Ar ′ represents an aromatic ring group.
m represents an integer of 1 or more.
Resin (B) may be used individually by 1 type, and may use 2 or more types together.
The content of the resin (B) in the total solid content of the composition of the present invention is generally often 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more. Although an upper limit in particular is not restrict | limited, 99 mass% or less is preferable, 90 mass% or less is more preferable, and 85 mass% or less is still more preferable.
Preferred examples of the resin (B) include the resins disclosed in paragraphs [0142] to [0347] of US Patent Application Publication No. 2016 / 0282720A1.

  The composition of the present invention may contain both the resin (A) and the resin (B).

<Photoacid generator (C)>
The composition of the present invention typically contains a photoacid generator (hereinafter also referred to as “photoacid generator (C)”).
The photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation.
As a photo-acid generator, the compound which generate | occur | produces an organic acid by irradiation of actinic light or a radiation is preferable. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.

  As the photoacid generator, known compounds that generate an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs [0125] to [0319] of US Patent Application Publication No. 2016 / 0070167A1, paragraphs [0086] to [0094] of US Patent Application Publication No. 2015 / 0004544A1, and US Patent Application Publication No. 2016 / Known compounds disclosed in paragraphs [0323] to [0402] of No. 0237190A1 can be suitably used as the photoacid generator (C).

  As a photo-acid generator (C), the compound represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) is preferable, for example.

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} are generally from 1 to 30, 1 to 20 are preferred.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group) and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —.
Z ⁻ represents an anion.

Preferable embodiments of the cation in the general formula (ZI) include corresponding groups in the compound (ZI-1), the compound (ZI-2), the compound (ZI-3), and the compound (ZI-4) described later. .
The photoacid generator (C) may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (ZI) and at least one of R _{201 to} R ₂₀₃ of the other compound represented by the general formula (ZI) are a single bond. Alternatively, it may be a compound having a structure bonded through a linking group.

First, the compound (ZI-1) will be described.
The compound (ZI-1) is at least one of the aryl groups _R 201 _{to R 203} in formula (ZI), arylsulfonium compounds, i.e., compounds containing an arylsulfonium as a cation.
Arylsulfonium _compound, all of R 201 _{to R 203} may be an aryl group _{or a} part of R 201 _{to R 203} is an aryl group and the remainder may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

The aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. The cycloalkyl group is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, or the like.

The aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ are each independently an alkyl group (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), or an aryl group (eg, carbon Formula 6-14), an alkoxy group (for example, C1-15), a halogen atom, a hydroxyl group, or a phenylthio group may be included as a substituent.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group or 2-oxocyclo group. An alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, and pentyl group) and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

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

In general formula (ZI-3),
R _{1c to} R _5c are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. The ring structure may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include a 3- to 10-membered ring, a 4- to 8-membered ring is preferable, and a 5- or 6-membered ring is more preferable.

Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by combining R _5c and R _6c , and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
Zc ^- represents an anion.

Next, the compound (ZI-4) will be described.
The compound (ZI-4) is represented by the following general formula (ZI-4).

In general formula (ZI-4),
l represents an integer of 0-2.
r represents an integer of 0 to 8.
R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have a substituent.
R ₁₄ represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. These groups may have a substituent. When a plurality of R ₁₄ are present, they each independently represent the above group such as a hydroxyl group.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, the ring skeleton may contain an oxygen atom or a heteroatom such as a nitrogen atom. In one embodiment, it is preferred that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure.
Z ⁻ represents an anion.

In General Formula (ZI-4), the alkyl groups of R ₁₃ , R _14, and R ₁₅ are linear or branched. As for carbon number of an alkyl group, 1-10 are preferable. As the alkyl group, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like is more preferable.

Next, general formulas (ZII) and (ZIII) will be described.
In formula (ZII), and _{(ZIII), R} 204 ~R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group for R _{204 to} R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R _{204 to} R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group of R ₂₀₄ to R _207, a linear alkyl group or branched alkyl group having 3 to 10 carbon atoms having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, A butyl group and a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) are preferable.

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may each independently have a substituent. Aryl group R ₂₀₄ to R _207, examples of the alkyl group, and a substituent which may have a cycloalkyl group, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (e.g. 3 carbon 15), an aryl group (eg, having 6 to 15 carbon atoms), an alkoxy group (eg, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents an anion.

Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in the general formula (ZI-4) ^- as the following general formula (3) The anion represented is preferred.

In general formula (3),
o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. 1-10 are preferable and, as for carbon number of this alkyl group, 1-4 are more preferable. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xf are fluorine atoms.

R ₄ and R ₅ each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₄ and R ₅ are present, R ₄ and R ₅ may be the same as or different from each other.
The alkyl group represented by R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are preferably a hydrogen atom.
Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (3).

L represents a divalent linking group. When a plurality of L are present, L may be the same or different.
Examples of the divalent linking group include —COO — (— C (═O) —O—), —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, — SO—, —SO ₂ —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a combination thereof And divalent linking groups. Among them, -COO -, - OCO -, - CONH -, - NHCO -, - CO -, - O -, - SO 2 -, - COO- alkylene group -, - OCO- alkylene group -, - CONH- alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.

W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable.
Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable.

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring that does not have aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the aforementioned resin. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is preferable.

  The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), a cycloalkyl group (monocyclic, polycyclic and spirocyclic). Any may be sufficient, C3-C20 is preferable), an aryl group (C6-C14 is preferable), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide Groups, and sulfonate groups. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

Formula (3) As the anion represented ^{_{by, SO 3 - -CF 2 -CH 2}} -OCO- (L) q'-W, SO 3 - -CF 2 -CHF-CH 2 -OCO- (L) ^{_{q'-W, SO 3 - -CF}} 2 -COO- (L) q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q-W, or, SO ₃ ^- _{-CF 2 -CH (CF 3) -OCO-} (L) q'-W is preferred. Here, L, q, and W are the same as those in the general formula (3). q ′ represents an integer of 0 to 10.

In one embodiment, Z in formula (ZI) ^-, Z in the general formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in the general formula (ZI-4) ^- as is generally the following An anion represented by the formula (4) is also preferable.

In general formula (4),
X ^B1 and X ^B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms.
X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. Preferably, at least one of X ^B3 and X ^B4 is a fluorine atom or a monovalent organic group having a fluorine atom, and both X ^B3 and X ^B4 are a monovalent organic group having a fluorine atom or a fluorine atom. Is more preferable. More preferably, both X ^B3 and X ^B4 are alkyl groups substituted with fluorine.
L, q and W are the same as those in the general formula (3).

Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in the general formula (ZI-4) ^- may be a benzenesulfonic acid anion Often, a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group is preferred.

Z in the general formula (ZI) ^-, the formula Z in (ZII) ^-, Zc in formula (ZI-3) ^- Z in, and the general formula (ZI-4) ^- The following general formula (SA1) An aromatic sulfonate anion represented by the formula is also preferable.

In formula (SA1),
Ar represents an aryl group, and may further have a substituent other than the sulfonate anion and the — (D—B) group. Furthermore, examples of the substituent that may be included include a fluorine atom and a hydroxyl group.

  n represents an integer of 0 or more. As n, 1-4 are preferable, 2-3 are more preferable, and 3 is still more preferable.

  D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfonic acid group, a sulfonic acid ester group, an ester group, and a group composed of a combination of two or more thereof.

  B represents a hydrocarbon group.

  Preferably, D is a single bond and B is an aliphatic hydrocarbon structure. B is more preferably an isopropyl group or a cyclohexyl group.

  Preferred examples of the sulfonium cation in general formula (ZI) and the iodonium cation in general formula (ZII) are shown below.

Preferred examples of anion Z ⁻ in general formula (ZI), general formula (ZII), Zc ⁻ in general formula (ZI-3), and Z ⁻ in general formula (ZI-4) are shown below.

  Any of the above cations and anions can be used in combination as a photoacid generator.

The photoacid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
The photoacid generator is preferably in the form of a low molecular compound.
When the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
When the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above or may be incorporated in a resin different from the resin (A). .
A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
The content of the photoacid generator in the composition (when there are a plurality of types) is preferably 0.1 to 35% by mass, and preferably 0.5 to 25% by mass based on the total solid content of the composition. Is more preferable, 3-20 mass% is still more preferable, and 3-15 mass% is especially preferable.
When the compound represented by the above general formula (ZI-3) or (ZI-4) is included as the photoacid generator, the content of the photoacid generator contained in the composition (if there are multiple types, The total) is preferably 5 to 35 mass%, more preferably 7 to 30 mass%, based on the total solid content of the composition.

<Acid diffusion control agent (D)>
The composition of the present invention preferably contains an acid diffusion controller (D). The acid diffusion controller (D) acts as a quencher that traps the acid generated from the photoacid generator and the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, an onium salt (DC) that becomes a weak acid relative to an acid generator, a nitrogen atom A low molecular weight compound (DD) having a group capable of leaving by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation moiety can be used as an acid diffusion controller. In the composition of the present invention, a known acid diffusion controller can be used as appropriate. For example, Paragraphs [0627] to [0664] of US Patent Application Publication No. 2016 / 0070167A1, Paragraphs [0095] to [0187] of US Patent Application Publication No. 2015 / 0004544A1, US Patent Application Publication No. 2016 / 0237190A1. Known compounds disclosed in paragraphs [0403] to [0423] of the specification and paragraphs [0259] to [0328] of U.S. Patent Application Publication No. 2016 / 0274458A1 are suitable as the acid diffusion control agent (D). Can be used for

  As the basic compound (DA), compounds having structures represented by the following formulas (A) to (E) are preferable.

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

The alkyl group in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

  As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like are preferable, imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, A compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, or the like is more preferable.

  A basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (DB)”) has a proton acceptor functional group, and has an actinic ray or It is a compound that decomposes upon irradiation with radiation and whose proton acceptor property is lowered, disappears, or changes from proton acceptor property to acidity.

  The proton acceptor functional group is a functional group having electrons or a group capable of electrostatically interacting with protons, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π conjugate. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to. 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 formula.

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

The compound (DB) is decomposed by irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property is reduced or lost, or the proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid property is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Means that when a proton adduct is formed from a compound having a proton acceptor functional group (DB) and a proton, the equilibrium constant in its chemical equilibrium is decreased.
Proton acceptor property can be confirmed by measuring pH.

  The acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) upon irradiation with actinic rays or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1, − More preferably, 13 <pKa <-3 is satisfied.

  The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in, 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 the value of acid dissociation constant pKa is low. Specifically, the acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can be used to calculate a value based on a Hammett substituent constant and a database of known literature values. 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).

In the composition of the present invention, an onium salt (DC) that is a weak acid relative to the photoacid generator can be used as an acid diffusion controller.
When a photoacid generator and an onium salt that generates an acid that is relatively weak with respect to the acid generated from the photoacid generator are mixed and used, the photoacid generator is generated by irradiation with actinic rays or radiation. When the acid generated from the acid collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion. 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.

  As the onium salt that is a weak acid relative to the photoacid generator, compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.

In the formula, R ⁵¹ represents a hydrocarbon group which may have a substituent, and Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. Each of the M ⁺ is independently an ammonium cation, a sulfonium cation or an iodonium cation.

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

An onium salt (DC), which is a weak acid relative to the photoacid generator, has a cation moiety and an anion moiety in the same molecule, and is a compound in which the cation moiety and the anion moiety are linked by a covalent bond ( (Hereinafter also referred to as “compound (DCA)”).
As the compound (DCA), a compound represented by any one of the following general formulas (C-1) to (C-3) is preferable.

In general formulas (C-1) to (C-3),
R ₁ , R ₂ , and R ₃ each independently 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 -, and ^-N. R ₄ has a carbonyl group (—C (═O) —), a sulfonyl group (—S (═O) ₂ —), and a sulfinyl group (—S (═O) — at the linking site with the adjacent N atom. ) Represents a monovalent substituent having at least one.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be bonded to each other to form a ring structure. In General Formula (C-3), two of R _{1 to} R ₃ may be combined to represent one divalent substituent, and may be bonded to an N atom by a double bond.

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. An alkyl group, a cycloalkyl group, or an aryl group is preferable.

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 these 2 Examples include groups formed by combining more than one species. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more thereof.

A low molecular compound (DD) having a nitrogen atom and a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (DD)”) has a group leaving on the nitrogen atom by the action of an acid. It is preferable that it is an amine derivative having.
The group capable of leaving by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and more preferably a carbamate group or a hemiaminal ether group. .
100-1000 are preferable, as for the molecular weight of a compound (DD), 100-700 are more preferable, and 100-500 are still more preferable.
Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group is represented by the following general formula (d-1).

In general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group ( Preferably it represents C1-C10) or an alkoxyalkyl group (preferably C1-C10). Rb may be connected to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Rb are each independently a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group, or It may be substituted with a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, a cycloalkyl group, or an aryl group, and more preferably a linear or branched alkyl group or a cycloalkyl group.
Examples of the ring formed by connecting two Rb to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
Specific examples of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph [0466] of US 2012/0135348 A1.

  The compound (DD) preferably has a structure represented by the following general formula (6).

In general formula (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb is synonymous with Rb in the general formula (d-1), and preferred examples are also the same.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are each independently substituted with the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb. A good group may be substituted with the same group as described above.

Specific examples of the Ra alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) include the same groups as those described above for Rb. It is done.
Specific examples of the particularly preferred compound (DD) in the present invention include, but are not limited to, compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012 / 0135348A1.

The onium salt compound (DE) having a nitrogen atom in the cation part (hereinafter also referred to as “compound (DE)”) is preferably a compound having a basic site containing a nitrogen atom in the cation part. The basic moiety is preferably an amino group, and more preferably an aliphatic amino group. More preferably, all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly connected to the nitrogen atom.
Preferable specific examples of compound (DE) include, but are not limited to, the compounds disclosed in paragraph [0203] of US Patent Application Publication No. 2015 / 03009408A1.

  Preferred examples of the acid diffusion controller (D) are shown below.

In the composition of the present invention, the acid diffusion controller (D) may be used alone or in combination of two or more.
The content of the acid diffusion controller (D) in the composition (when there are multiple types, the total thereof) is preferably 0.1 to 10% by mass, based on the total solid content of the composition, 5 mass% is more preferable.

<Hydrophobic resin (E)>
The composition of the present invention may contain a hydrophobic resin (E). The hydrophobic resin (E) is preferably a resin different from the resin (A) and the resin (B).
When the composition of the present invention contains the hydrophobic resin (E), the static / dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid follow-up in immersion exposure, reduce immersion defects, and the like.
The hydrophobic resin (E) is preferably designed to be unevenly distributed on the surface of the resist film. However, unlike the surfactant, the hydrophobic resin (E) is not necessarily required to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

The hydrophobic resin (E) is selected from the group consisting of “fluorine atoms”, “silicon atoms”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the surface layer of the membrane. It is preferable that the resin has a repeating unit having at least one kind.
When the hydrophobic resin (E) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin, It may be contained in the chain.

  When the hydrophobic resin (E) 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 hydrophobic resin (E) preferably has at least one group selected from the following groups (x) to (z).
(X) Acid group (y) A group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer (hereinafter also referred to as a polar conversion group)
(Z) a group decomposable by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) ) And a methylene group.
The acid group is preferably a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis (alkylcarbonyl) methylene group.

Examples of the group (y) that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer include a lactone group, a carboxylic acid ester group (—COO—), and an acid anhydride group (—C (O) OC. (O) -), an acid imide group (-NHCONH-), a carboxylic acid thioester group (-COS-), a carbonic acid ester group (-OC (O) O-), sulfate group (-OSO ₂ O-), and Examples thereof include a sulfonic acid ester group (—SO ₂ O—), and a lactone group or a carboxylic acid ester group (—COO—) is preferable.
The repeating unit containing these groups is, for example, a repeating unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include a repeating unit of an acrylate ester and a methacrylate ester. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has these groups at the time of superposition | polymerization.
Examples of the repeating unit having a lactone group include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).

  The content of the repeating unit having a group (y) that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is 1 to 100 mol% based on all repeating units in the hydrophobic resin (E). Is preferable, 3-98 mol% is more preferable, 5-95 mol% is still more preferable.

Examples of the repeating unit having a group (z) that is decomposed by the action of an acid in the hydrophobic resin (E) are the same as the repeating unit having an acid-decomposable group mentioned in the resin (A). The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the hydrophobic resin (E). 20-60 mol% is still more preferable.
The hydrophobic resin (E) may further have a repeating unit different from the above-described repeating unit.

  10-100 mol% is preferable with respect to all the repeating units in hydrophobic resin (E), and, as for the repeating unit containing a fluorine atom, 30-100 mol% is more preferable. Moreover, 10-100 mol% is preferable with respect to all the repeating units in hydrophobic resin (E), and, as for the repeating unit containing a silicon atom, 20-100 mol% is more preferable.

On the other hand, particularly when the hydrophobic resin (E) contains a CH ₃ partial structure in the side chain portion, a mode in which the hydrophobic resin (E) does not substantially contain a fluorine atom and a silicon atom is also preferable. Moreover, it is preferable that hydrophobic resin (E) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom.

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

  0.01-5 mass% is preferable and, as for the total content of the residual monomer and / or oligomer component contained in hydrophobic resin (E), 0.01-3 mass% is more preferable. Further, the dispersity (Mw / Mn) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.

  As hydrophobic resin (E), well-known resin can be used selecting it suitably as independent or those mixtures. For example, known resins disclosed in paragraphs [0451] to [0704] of US Patent Application Publication No. 2015 / 0168830A1 and paragraphs [0340] to [0356] of United States Patent Application Publication No. 2016 / 0274458A1. Can be suitably used as the hydrophobic resin (E). The repeating units disclosed in paragraphs [0177] to [0258] of US Patent Application Publication No. 2016 / 0237190A1 are also preferable as the repeating units constituting the hydrophobic resin (E).

  Preferred examples of the monomer corresponding to the repeating unit constituting the hydrophobic resin (E) are shown below.

Hydrophobic resin (E) may be used individually by 1 type, and may use 2 or more types together.
It is preferable to use a mixture of two or more kinds of hydrophobic resins (E) having different surface energies from the viewpoint of compatibility between the immersion liquid followability and the development characteristics in the immersion exposure.
0.01-10 mass% is preferable with respect to the total solid in the composition of this invention, and, as for content in the composition of hydrophobic resin (E), 0.05-8 mass% is more preferable.

<Solvent (F)>
The composition of the present invention may contain a solvent.
In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs [0665] to [0670] of US Patent Application Publication No. 2016 / 0070167A1, paragraphs [0210] to [0235] of US Patent Application Publication No. 2015 / 0004544A1, US Patent Application Publication No. 2016 / 0237190A1. Known solvents disclosed in paragraphs [0424] to [0426] of the specification and paragraphs [0357] to [0366] of US Patent Application Publication No. 2016 / 0274458A1 can be suitably used.
Examples of the solvent that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), Examples include organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate, which may have a ring.

As an organic solvent, you may use the mixed solvent which mixed the solvent which has a hydroxyl group in a structure, and the solvent which does not have a hydroxyl group.
As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-described exemplary compounds can be selected as appropriate. As the solvent containing a hydroxyl group, an alkylene glycol monoalkyl ether, an alkyl lactate or the like is preferable, and propylene glycol monomethyl ether ( PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferable. Further, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate, etc. are preferable. Among these, propylene More preferred are glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, More preferred are cyclohexanone, cyclopentanone or 2-heptanone. As the solvent having no hydroxyl group, propylene carbonate is also preferable.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40. preferable. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in terms of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, may be a propylene glycol monomethyl ether acetate single solvent, or may be two or more mixed solvents containing propylene glycol monomethyl ether acetate.

<Crosslinking agent (G)>
The composition of this invention may contain the compound (henceforth a crosslinking agent (G)) which bridge | crosslinks resin by the effect | action of an acid. As the crosslinking agent (G), a known compound can be appropriately used. For example, known compounds disclosed in paragraphs [0379] to [0431] of US Patent Application Publication No. 2016 / 0147154A1 and paragraphs [0064] to [0141] of US Patent Application Publication No. 2016 / 0282720A1 Can be suitably used as the crosslinking agent (G).
The crosslinking agent (G) is a compound having a crosslinkable group capable of crosslinking the resin, and examples of the crosslinkable group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, And an oxetane ring.
The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring.
The crosslinker (G) is preferably a compound (including a resin) having two or more crosslinkable groups.
The cross-linking agent (G) is more preferably a phenol derivative, a urea compound (a compound having a urea structure) or a melamine compound (a compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.
A crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
1-50 mass% is preferable with respect to the total solid of a resist composition, content of a crosslinking agent (G) has preferable 3-40 mass%, and 5-30 mass% is still more preferable.

<Surfactant (H)>
The composition of the present invention may contain a surfactant. When a surfactant is included, a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) Is preferred.

When the composition of the present invention contains a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used, a pattern having good adhesion and development defects with good sensitivity and resolution can be obtained.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph [0276] of US Patent Application Publication No. 2008/0248425.
In addition, surfactants other than fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more.
When the composition of this invention contains surfactant, 0.0001-2 mass% is preferable with respect to the total solid of a composition, and 0.0005-1 mass% is more with respect to the total solid content of a composition. preferable.
On the other hand, when the content of the surfactant is 10 ppm or more based on the total solid content of the composition, the surface uneven distribution of the hydrophobic resin (E) is increased. Thereby, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and water followability at the time of immersion exposure is improved.

(Other additives)
The composition of the present invention may further contain an acid proliferation agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, or a dissolution accelerator.

<Preparation method>
1.0-10 mass% is preferable, as for the solid content concentration of the composition of this invention, 2.0-5.7 mass% is more preferable, and 2.0-5.3 mass% is still more preferable. The solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.

  The film thickness of the actinic ray-sensitive or radiation-sensitive film made of the composition of the present invention is preferably 90 nm or less, more preferably 85 nm or less, from the viewpoint of improving resolution. 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 or film forming property.

  The composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent, filtering the solution, and applying the solution on a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less. This filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Laid-Open No. 2002-62667), cyclic filtration may be performed, and a plurality of types of filters may be connected in series or in parallel. It may be connected to and filtered. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration.

<Application>
The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition that changes its properties upon reaction with irradiation with actinic rays or radiation. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), circuit boards such as liquid crystals or thermal heads, fabrication of imprint mold structures, other photofabrication processes, or The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition. The pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, a MEMS (Micro Electro Mechanical Systems), and the like.

[Pattern formation method]
The present invention also relates to a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern formation method of this invention is demonstrated. In addition to the description of the pattern forming method, the actinic ray-sensitive or radiation-sensitive film of the present invention will also be described.

The pattern forming method of the present invention comprises:
(I) a step of forming a resist film (actinic light sensitive or radiation sensitive film) on a support with the above-mentioned actinic ray sensitive or radiation sensitive resin composition (resist film forming step);
(Ii) exposing the resist film (irradiating actinic rays or radiation) (exposure step); and
(Iii) a step of developing the exposed resist film using a developer (development step),
Have

The pattern formation method of the present invention is not particularly limited as long as it includes the steps (i) to (iii) above, and may further include the following steps.
In the pattern forming method of the present invention, (ii) the exposure method in the exposure step may be immersion exposure.
The pattern forming method of the present invention preferably includes (ii) a pre-heating (PB: PreBake) step before (ii) the exposure step.
The pattern forming method of the present invention preferably includes (v) a post-exposure bake (PEB) step after (ii) the exposure step and (iii) before the development step.
The pattern forming method of the present invention may include (ii) an exposure step a plurality of times.
The pattern forming method of the present invention may include (iv) a preheating step a plurality of times.
The pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.

In the pattern forming method of the present invention, the above-described (i) film formation step, (ii) exposure step, and (iii) development step can be performed by a generally known method.
If necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support. As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (top coat) may be formed on the upper layer of the resist film. As the protective film, a known material can be appropriately used. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, U.S. Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016 / 157988A can be suitably used. As a composition for protective film formation, what contains the acid diffusion control agent mentioned above is preferable.
A protective film may be formed on the resist film containing the hydrophobic resin described above.

The support is not particularly limited, and is generally used in a manufacturing process of a semiconductor such as an IC, or a manufacturing process of a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes. A substrate can be used. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ , and SiN.

The heating temperature is preferably 70 to 130 ° C, more preferably 80 to 120 ° C in both (iv) the preheating step and (v) the post-exposure heating step.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds in both (iv) the preheating step and (v) the post-exposure heating step.
The heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed using a hot plate or the like.

Although there is no restriction | limiting in the light source wavelength used for an exposure process, For example, infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-ray | X_line, an electron beam, etc. are mentioned. Among these, far ultraviolet light is preferable, and the wavelength is preferably 250 nm or less, more preferably 220 nm or less, and further preferably 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., KrF excimer laser, ArF excimer laser, EUV or electron beam is preferred.

  (Iii) In the development step, an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer) may be used.

As the alkali developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used. In addition, an alkaline aqueous solution such as an inorganic alkali, a primary to tertiary amine, an alcohol amine, and a cyclic amine can also be used. It can be used.
Furthermore, the alkaline developer may contain an appropriate amount of alcohols and / or surfactant. The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkaline developer is usually 10-15.
The time for developing with an alkali developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.

  The organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Is preferred.

  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, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, 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, butane Examples include butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

  As the alcohol solvent, the amide solvent, the ether solvent, and the hydrocarbon solvent, the solvents disclosed in paragraphs [0715] to [0718] of US Patent Application Publication No. 2016 / 0070167A1 can be used.

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably substantially free of moisture.
The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. % Is particularly preferred.

  The organic developer may contain an appropriate amount of a known surfactant as required.

  The content of the surfactant 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 developer may contain the acid diffusion control agent described above.

  As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and left stationary for a certain time (paddle method), Examples include a method of spraying developer on the surface (spray method) or a method of continuously discharging developer while scanning a developer discharge nozzle on a substrate rotating at a constant speed (dynamic dispensing method). It is done.

  A step of developing using an aqueous alkali solution (alkali developing step) and a step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined. As a result, since the pattern can be formed without dissolving only the intermediate exposure intensity region, a finer pattern can be formed.

  (Iii) It is preferable to include the process (rinsing process) wash | cleaned using the rinse liquid after a image development process.

  As the rinsing solution used in the rinsing step after the developing step using an alkali developer, pure water can be used, for example. The pure water may contain an appropriate amount of a surfactant. In this case, after the developing process or the rinsing process, a process for removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid may be added. Further, after the rinse treatment or the treatment with the supercritical fluid, a heat treatment may be performed in order to remove moisture remaining in the pattern.

There is no particular limitation on the rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent, as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. As the rinse liquid, use a rinse 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. Is preferred.
Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent are the same as those described in the developer containing an organic solvent.
As the rinse liquid used in the rinse step in this case, a rinse liquid containing a monohydric alcohol is more preferable.

  Examples of the monohydric alcohol used in the rinsing step include linear, branched, or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 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 methyl isobutyl carbinol. Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl isobutyl carbinol. .

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 still more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The rinse solution may contain an appropriate amount of a surfactant.
In the rinsing step, the substrate that has been developed using the organic developer is washed with a rinse containing an organic solvent. The method of the cleaning process 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), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method (spray method) of spraying a rinsing liquid on the substrate surface. In particular, it is preferable to perform a cleaning process by a spin coating method, rotate the substrate at a rotational speed of 2,000 to 4,000 rpm after cleaning, and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. By this heating process, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is usually 40 to 160 ° C, preferably 70 to 95 ° C, the heating time is usually 10 seconds to 3 minutes, and preferably 30 seconds to 90 seconds.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developer, a rinse solution, an antireflection film-forming composition, or The topcoat-forming composition or the like) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above various materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and substantially not (less than the detection limit of the measuring device). Is particularly preferred.

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. The filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. 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. As the filter, a filter in which the amount of eluate is reduced as disclosed in Japanese Patent Application Publication No. 2006-201426 (Japanese Patent Laid-Open No. 2014-201426) is preferable.
In addition to filter filtration, impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2006-206500 (Japanese Patent Laid-Open No. 2006-206500).
Moreover, 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. Alternatively, a method of performing distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) or the like can be mentioned. The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.

  The various materials described above are described in U.S. Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351), etc., in order to prevent contamination by impurities. Preferably, it is stored in a separate container.

A method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. As a method for improving the surface roughness of the pattern, for example, a method of processing a pattern by a plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957 is cited. In addition, Japanese Patent Application Publication No. 2004-235468 (JP 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.
In addition, the pattern formed by the above method is, for example, a spacer process disclosed in Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as a core material (Core).

[Method of manufacturing electronic device]
The present invention also relates to an electronic device manufacturing method including the pattern forming method described above. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (for example, home appliances, OA (Office Automation) -related devices, media-related devices, optical devices, communication devices, etc.). Is done.

  Below, based on an Example, this invention is demonstrated still in detail. The materials, amounts used, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the following examples.

<Synthesis Example 1: Synthesis of Compound MA-1>
Below, the outline of the synthetic | combination procedure of compound MA-1 in an Example is shown.

(Synthesis of Compound (i))
To 350 ml of dehydrated THF (tetrahydrofuran), 416 mL of a THF solution containing 20% by mass of LDA (lithium diisopropylamide) was added, and the resulting solution was cooled to −78 ° C. At −78 ° C., 90 g of ethyl 2-ethylbutyrate (1) was added to this solution and the solution was stirred for 1 hour. Next, a solution obtained by dissolving 116 g of methyl paratoluenesulfonate in 52 ml of dehydrated THF was further added to the obtained solution. Thereafter, the resulting solution was stirred at 25 ° C. for 2 hours under a nitrogen atmosphere. After adding 300 g of water to this solution to stop the reaction, the organic phase was washed with 400 g of water five times. The obtained concentrated liquid was distilled under reduced pressure to remove the solvent to obtain 60 g of compound (i).

(Synthesis of Compound (ii))
To 411 ml of dehydrated THF, 28 g of magnesium and a piece of iodine were added. To the obtained solution, a solution obtained by dissolving 90 g of 1,4-dibromobutane in 411 ml of dehydrated THF was added dropwise. Thereafter, this solution was stirred at 25 ° C. for 1 hour under a nitrogen atmosphere. Next, a solution obtained by dissolving 60 g of compound (i) in 411 ml of dehydrated THF was added dropwise to the resulting solution. The obtained solution was stirred at 25 ° C. for 1 hour under a nitrogen atmosphere, and then 400 g of ammonium chloride aqueous solution was added to the solution to stop the reaction. The organic phase was separated and washed three times with 400 g of an aqueous ammonium chloride solution and water, and then the obtained concentrated solution was distilled under reduced pressure to remove the solvent to obtain 40 g of compound (ii).

(Synthesis of Compound MA-1)
40 g of compound (ii) was dissolved in 343 ml of dehydrated THF, and the resulting solution was cooled to -78 ° C. At −78 ° C., 147 ml of n-butyllithium (1.6M) was added dropwise to this solution, and the solution was stirred for 1 hour. Thereafter, 27 g of methacrylic acid chloride was added dropwise to the resulting solution, and the solution was stirred at 25 ° C. for 2 hours under a nitrogen atmosphere. 400 g of water was added to this solution to stop the reaction, and the organic phase was then washed with 400 g of water five times. The obtained concentrated liquid was distilled under reduced pressure to remove the solvent to obtain 25 g of compound MA-1.

<Synthesis of Resin (A-1)>
Under a nitrogen stream, 9.0 g of cyclohexanone was placed in a three-necked flask and the cyclohexanone was heated to 85 ° C.
Separately, 9.3 g of compound MA-1, 5.78 g of norbornane lactone methacrylate (compound MB-1), and 5 mol% of polymerization initiator V-601 (Wako Pure Chemical Industries, Ltd.) based on the total amount of these monomers. Was dissolved in 36 g of cyclohexanone to obtain a solution.
Subsequently, this solution was dripped at the said 3 necked flask over 4 hours. After completion of dropping, the reaction was further continued at 85 ° C. for 2 hours. The reaction solution was allowed to cool and then diluted with 40 g of cyclohexanone. The diluted solution was dropped into a mixed solution of 633 g of methanol / 70 g of water, and the precipitated powder was collected by filtration. The obtained powder was washed with a mixed solution of 90 g of methanol / 10 g of water, further filtered and dried to obtain 13 g of resin (A-1). The weight average molecular weight of the obtained resin (A-1) was 10,000 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.6.

  Similarly, other resins (A-2) to (A-15) shown below were synthesized.

  The structure of the monomer used for the synthesis of the resin (A) used in Examples and Comparative Examples is shown below. Table 1 below shows the molar ratio of repeating units in each resin, the weight average molecular weight (Mw), and the dispersity (Mw / Mn). Furthermore, the combination of the repeating unit which each resin (A-1)-(A-15) has is shown below.

  The structure of the photoacid generator (C) used in Examples and Comparative Examples is shown below.

  The structure of the acid diffusion controller (D) used in the examples and comparative examples is shown below.

  The structure of the hydrophobic resin (E) used in Examples and Comparative Examples is shown below. Table 2 below shows the composition ratio (molar ratio; corresponding to the order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn) of the repeating units in each resin.

The solvent (F) used by the Example and the comparative example is shown below.
F-1: Propylene glycol monomethyl ether acetate (PGMEA)
F-2: Ethyl lactate F-3: Propylene glycol monomethyl ether (PGME)
F-4: Cyclohexanone F-5: γ-Butyrolactone

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
Each component shown in Table 3 below was mixed so that the solid content concentration was 4% by mass to prepare an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as a resin composition). Solid content here means all components other than a solvent (F). It mix | blended so that solid content might become a ratio according to the mass part shown in Table 3. The resin composition was filtered in the order of a polyethylene filter having a pore size of 50 nm, a nylon filter having a pore size of 10 nm, and finally a polyethylene filter having a pore size of 5 nm. Finally, the resin composition obtained as a filtrate was used in Examples and Comparative Examples.

<Pattern formation: ArF immersion exposure, organic solvent development>
An organic antireflection film-forming composition ARC29SR (manufactured by Brewer Science) was applied onto a silicon wafer, and the silicon wafer coated with the organic antireflection film-forming composition was baked at 205 ° C. for 60 seconds to obtain a film thickness of 98 nm. An antireflection film was formed. Then, the resin compositions of Examples and Comparative Examples shown in Table 3 were applied and baked at 100 ° C. for 60 seconds to form an actinic ray-sensitive or radiation-sensitive film (resist film) having a film thickness of 90 nm. did.
Using the ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.730, inner sigma 0.630, XY deflection) on the obtained resist film Exposure was through a 6% halftone mask with a 1: 1 line and space pattern with a width of 75 nm. As the immersion liquid, ultrapure water was used.
The exposed resist film was baked at 120 ° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then rinsed with 4-methyl-2-pentanol for 30 seconds. Thereafter, this was spin-dried to obtain a negative pattern.

<Performance evaluation>
The obtained pattern was evaluated by the method shown below. The evaluation results are shown in Table 4.

[Line width roughness (LWR, nm)]
When the resolved 75 nm (1: 1) line-and-space pattern is observed from above the pattern using a length-measuring scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)) The width was observed at an arbitrary point (160 points), and the measurement variation was evaluated by 3σ. The smaller the value of the LWR, the less the fluctuation of the pattern line width and the better the performance.

From Table 4, the Example using the actinic-ray-sensitive or radiation-sensitive resin composition containing resin which has a repeating unit which has group represented by General formula (1) is represented by General formula (1). Compared with the comparative example using the actinic-ray-sensitive or radiation-sensitive resin composition containing resin which does not have a repeating unit which has group, it was confirmed that LWR is favorable.
From comparison between Example 10 and Example 11, it was confirmed that when X in the general formula (2) is a single bond (Example 10), better LWR is exhibited.
From the comparison of Examples 1, 2, and 9, it was confirmed that the cyclic structure formed by Z in the general formula (1) together with the carbon atom is more preferably an alicyclic structure having 5 or 6 carbon atoms.

  It was confirmed that a pattern having a good LWR can be obtained even when ArF exposure is performed on the resist film formed in the above example and alkali development is performed on the exposed film. Similarly, even when the resist film formed in the above embodiment is subjected to KrF exposure, electron beam exposure, or EUV exposure, and the exposed film is subjected to alkali development or organic solvent development, It was confirmed that a pattern with a good LWR could be obtained.

Claims (10)

An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit having a group represented by the following general formula (1).

In general formula (1), R ₁ , R ₂ and R ₃ each independently represents a chain alkyl group. Here, the total number of carbon atoms contained in R ₁ , R ₂ and R ₃ is 5 or more. Z represents a group that forms a monocyclic or polycyclic ring structure with a carbon atom. * Represents a binding position. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit is a repeating unit represented by the following general formula (2).

In general formula (2), R represents a hydrogen atom, a halogen atom, or an organic group. X represents a single bond or a divalent linking group. R ₁ , R ₂ , R ₃ and Z are the same as those in the general formula (1).   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein X is a single bond.   The actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-3 whose Z is group which forms a monocyclic alicyclic structure with a carbon atom.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein the alicyclic structure is an alicyclic structure having 5 or 6 carbon atoms. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein R ₁ is a chain alkyl group having 3 or more carbon atoms. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein R ₁ and R ₂ are each independently a chain alkyl group having 2 or more carbon atoms.   The resist film formed with the actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-7. A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7;
An exposure step of exposing the resist film;
And a developing step of developing the exposed resist film using a developer.   The manufacturing method of an electronic device containing the pattern formation method of Claim 9.