JP6818600B2 - Actinic light-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, manufacturing method of electronic device - Google Patents

Description

The present invention relates to an actinic or radiation sensitive resin composition, a resist film, a pattern forming method, and a method for producing an electronic device.

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), fine particles are obtained by lithography using a sensitive light-sensitive or radiation-sensitive resin composition. Processing is being carried out.
For example, Patent Document 1 discloses a pattern forming method using a resin having a predetermined repeating unit.

International Publication No. 2016/05/2313

When the present inventors examined the sensitive light-sensitive or radiation-sensitive resin composition specifically described in the Example column of Patent Document 1, they formed the sensitive light-sensitive or radiation-sensitive resin composition. It was found that there is room for improvement in the pattern line width (LWR (line width roughness)).

An object of the present invention is to provide a sensitive light-sensitive or radiation-sensitive resin composition capable of obtaining a pattern having excellent LWR performance.
Another object of the present invention is to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned actinic cheilitis or radiation-sensitive resin composition.

As a result of diligent 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 was found that the above problem can be solved by the following configuration.

(1) A sensitive light-sensitive or radiation-sensitive resin composition containing a resin having a repeating unit having a group represented by the general formula (1) described later.
(2) The actinic light-sensitive or radiation-sensitive resin composition according to (1) above, wherein the repeating unit is a repeating unit represented by the general formula (2) described later.
(3) The actinic or radiation-sensitive resin composition according to (2) above, wherein X in the general formula (2) described later is a single bond.
(4) The actinic cheilitis according to any one of (1) to (3) above, wherein Z in the general formula (1) described later is a group forming a monocyclic alicyclic structure together with a carbon atom. Radiation-sensitive resin composition.
(5) The actinic light-sensitive or radiation-sensitive resin composition according to (4) above, wherein the alicyclic structure is an alicyclic structure having 5 or 6 carbon atoms.
(6) The actinic cheilitis or radiation-sensitive property according to any one of (1) to (5) above, 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 feeling according to any one of (1) to (5) above, wherein R ₁ and R ₂ in the general formula (1) described later are independently chain alkyl groups having 2 or more carbon atoms. Active light or radiation sensitive resin composition.
(8) A resist film formed of the actinic 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 cheilitis or radiation-sensitive resin composition according to any one of (1) to (7) above.
The exposure process for exposing the resist film and
A pattern forming method including a developing step of developing the exposed resist film with a developing solution.
(10) A method for manufacturing an electronic device, including the pattern forming method according to (9) above.

According to the present invention, it is possible to provide a sensitive light-sensitive or radiation-sensitive resin composition capable of obtaining a pattern having excellent LWR performance.
Further, according to the present invention, it is possible to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes a group having a substituent as well as a group having no 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). Further, the "organic group" in the present specification means a group containing at least one carbon atom.
As used herein, the term "active light" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X rays, and electron beams (EB). : Electron Beam) and the like. As used herein, "light" means active light or radiation.
Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, EUV light, etc., but also electron beams and It also includes drawing with particle beams such as ion beams.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

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

[Actinic cheilitis or radiation-sensitive resin composition]
The actinic 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, and may be a positive type resist composition or a negative type resist composition. Further, it may be a resist composition for alkaline development or a resist composition for organic solvent development.
The composition of the present invention is typically a chemically amplified resist composition.

A feature of the composition of the present invention is that it contains 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, it is possible to form a pattern in which the fluctuation of the pattern line width (LWR) is particularly small.
The details of this mechanism are not clear, but it is speculated 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 a predetermined value or more. 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) becomes a bulky structure. As a result, the action of the acid facilitates decomposition between the oxygen atom and the carbon atom. Therefore, it is considered that the resist film made of the composition of the present invention has high photosensitivity and radiation sensitivity and exhibits excellent development contrast, so 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 the pattern formed by exposing and developing the resist film obtained from the composition is small.

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

<Resin (A)>
The composition of the present invention contains a resin having a repeating unit having a group represented by the 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 the bonding position.

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

Z represents a group that forms a monocyclic or polycyclic cyclic 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 heteroatom. Further, the cyclic structure may or may not exhibit 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 alicyclic structure of the monocyclic ring is not particularly limited, but 4 to 10 is preferable, 4 to 7 is more preferable, and 5 or 6 is further 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 in that the LWR is more excellent. As the polycyclic alicyclic structure, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group is preferable.

Among them, in that LWR is more excellent, Z preferably represents a group forming a monocyclic alicyclic structure together with a carbon atom. That is, it is preferable that the portion represented by Z is an alkylene group (preferably 3 to 9 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 4 or 5 carbon atoms).
The preferable range of the number of carbon atoms contained in the alicyclic structure of a single ring 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.
Among them, as the repeating unit having a group represented by the general formula (1), the repeating unit represented by the following general formula (2) is preferable because the 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 the 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 the general formula (2), X represents a single bond or a divalent linking group. The divalent linking groups include -COO- (-C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, and -SO-. , -SO _2- , alkylene group (preferably 1 to 6 carbon atoms), cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene group (preferably 2 to 6 carbon atoms), arylene group, and these. Examples include groups that combine a plurality of groups. Of 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- .

It is more preferable that X is 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 the resin can be synthesized by polymerizing the monomer containing the above structure.

The resin (A) may have one type of repeating unit having a group represented by the general formula (1) alone, or may have two or more types in combination.

The content of the repeating unit having a group represented by the general formula (1) in the resin (A) is not particularly limited, but 10 for all the repeating units in the resin (A) because the LWR is more excellent. It is preferably ~ 90 mol%, more preferably 20-80 mol%, further preferably 30-70 mol%, and particularly preferably 40-60 mol%.

Specific examples of the monomer corresponding to the repeating unit having a group represented by the general formula (1) will be given below, but the present invention is not limited to these specific examples.

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

It is also preferable that the resin (A) has the repeating unit described in paragraphs [0336] to [0369] of US Patent Application Publication No. 2016/0070167A1 as a repeating unit having another acid-degradable group.

Specific examples of the monomer corresponding to the repeating unit having another acid-degradable group will be given below, but the present invention is not limited to these specific examples.

The resin (A) may have one type of repeating unit having an acid-degradable group alone, or may have two or more types in combination.

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 a 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 fused to form a bicyclo structure or a spiro structure, or a 5 to 7-membered ring in the form of a bicyclo structure or a spiro structure. A sultone structure in which another ring structure is fused is more preferable.
The resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or any of the following general formulas (SL1-1) to (SL1-3). It is more preferred to have a repeating unit with the represented sultone structure. Further, the lactone structure or the sultone structure may be directly bonded to the main chain. Preferred structures include general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1). Examples thereof include a lactone structure represented by -21) and a sultone structure represented by the general formula (SL1-1).

The lactone-structured portion or the sultone-structured portion may or may not have a substituent (Rb ₂ ). Examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. A halogen atom, a hydroxyl group, a cyano group, an acid-degradable group or the like 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 from 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of existing substituents (Rb ₂ ) may be bonded to each other 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 above 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−, represents an integer of 0 to 5, is preferably 0 or 1, and more preferably 0. When n is 0, −R ₀ −Z− does not exist and a single bond is formed.
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's, each of them 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.
As Z, an ether bond or an ester bond is preferable, and an ester bond is more preferable.

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

In the general formula (A-1), _RA ¹ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
n represents an integer greater than or equal to 0.
R _A ² represents a substituent. When n is 2 or more, _RA ² independently represents a substituent.
A represents a single bond or a divalent linking group.
Z represents an atomic group forming a monocyclic structure or a polycyclic structure together with the group represented by -OC (= 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, as paragraphs [0370] to [0414] of U.S. Patent Application Publication No. 2016/0070167A1. It is also preferable to have the repeating unit described in 1.

The resin (A) may have a repeating unit 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 of them in combination. You may be.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and the specific example 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 hydrogen atoms and halogen atoms. , Or can be optionally substituted with a monovalent organic group.

In addition to the above-mentioned monomers, the following monomers are also preferably used as raw materials for the resin (A).

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

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.
As the repeating unit having a polar group, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group is preferable. Moreover, it is preferable that the repeating unit having a polar group does not have an acid-degradable 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 will be given below, but the present invention is not limited to these specific examples.

In addition, specific examples of the repeating unit having a polar group include the repeating unit disclosed in paragraphs [0415] to [0433] of US Patent Application Publication No. 2016/0070167A1.
The resin (A) may have one type of repeating unit having a polar group alone, or may have two or more types in combination.
The content of the repeating unit having a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 25 mol%, based on all the repeating units in the resin (A).

The resin (A) may further have a repeating unit that has neither an acid-degradable 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 monomers corresponding to repeating units having neither an acid-degradable group nor a polar group are shown below.

In addition, specific examples of the repeating unit having neither an acid-degradable group nor a polar group include the repeating unit disclosed in paragraph [0433] of U.S. Patent Application Publication No. 2016/0070167A1. ..
The resin (A) may have one type of repeating unit having 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 5 to 40 mol%, more preferably 5 to 30 mol%, based on all the repeating units in the resin (A). More preferably 5-25 mol%.

In addition to the above-mentioned repeating structural units, the resin (A) has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or resolution, heat resistance, sensitivity, etc., which are general necessary characteristics of resist. It may have various repeating structural units for the purpose of adjusting.
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. Examples include compounds.
In addition, an addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the various repeating structural units may be used.
In the resin (A), the 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, it is preferable that the resin (A) has substantially no aromatic group from the viewpoint of transmitting ArF light. More specifically, with respect to all the repeating units in the resin (A), the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally. Is more preferably 0 mol%, i.e. not having a repeating unit having an aromatic group. Further, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

It is preferable that all the repeating units of the resin (A) are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate-based repeating units, all of the repeating units are acrylate-based repeating units, and all of the repeating units are either methacrylate-based repeating units or acrylate-based 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 the 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 and 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. It is preferable to have a protected structure.
The content of the repeating unit having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, based on all the repeating units in the resin (A). , 50-100 mol% is more preferred.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, further preferably 3,000 to 15,000, and preferably 3,000 to 11,000. Especially preferable. 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.

The resin (A) may be used alone or in combination of two or more.
The content of the resin (A) in the total solid content of the composition of the present invention is generally 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. The upper limit is not particularly limited, but 99.5% by mass or less is preferable, 99% by mass or less is more preferable, and 97% by mass or less is further preferable.

<Resin (B)>
When the composition of the present invention contains a cross-linking 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 preferably formed.
The cross-linking agent (G) may be supported on the resin (B).
The resin (B) may have the above-mentioned acid-degradable group.

As the repeating unit having the phenolic hydroxyl group of the resin (B), the repeating unit represented by the following general formula (II) is preferable.

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.
The resin (B) may be used alone or in combination of two or more.
The content of the resin (B) in the total solid content of the composition of the present invention is generally 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.
Preferable 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 preferably contains a photoacid generator (hereinafter, also referred to as “photoacid generator (C)”).
A photoacid generator is a compound that generates an acid when irradiated with active light or radiation.
As the photoacid generator, a compound that generates an organic acid by irradiation with active light or radiation is preferable. Examples thereof 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, a known compound that generates an acid by irradiation with active light or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs [0125]-[0319] of U.S. Patent Application Publication 2016/0070167A1, paragraphs [0086]-[0094] of U.S. Patent Application Publication 2015/0004544A1, and U.S. Patent Application Publication 2016 / The known compounds disclosed in paragraphs [0323] to [0402] of 0237190A1 can be preferably used as the photoacid generator (C).

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

In the above general formula (ZI)
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The number of carbon atoms of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Further, two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, an alkylene group (e.g., butylene, pentylene) and _{-CH 2 -CH 2 -O-CH 2} -CH 2 - and the like.
Z ^- represents an anion.

Preferable embodiments of the cation in the general formula (ZI) include the corresponding groups in compound (ZI-1), compound (ZI-2), compound (ZI-3) and compound (ZI-4) described below. ..
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 the compounds R _{201 to} R ₂₀₃ represented by the general formula (ZI) and at least one of the other compounds R _{201 to} R ₂₀₃ represented by the general formula (ZI) are single-bonded. Alternatively, it may be a compound having a structure bonded via a linking group.

First, the compound (ZI-1) will be described.
The compound (ZI-1) is an aryl sulfonium compound in which at least one of R _{201 to} R ₂₀₃ of the above general formula (ZI) is an aryl group, that is, a compound having aryl sulfonium as a cation.
In the aryl sulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
Examples of the aryl sulfonium compound include a triaryl sulfonium compound, a diallyl alkyl sulfonium compound, an aryl dialkyl sulfonium compound, a diallyl cycloalkyl sulfonium compound, and an aryl dicycloalkyl sulfonium compound.

As the aryl group contained in the aryl sulfonium compound, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues and the like. When the aryl sulfonium 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 contained in the arylsulfonium compound as required is a linear alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms. Cycloalkyl group is preferable, and examples thereof include 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, and a cyclohexyl group.

The aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ are independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group (for example, carbon number). It may have an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

Next, the compound (ZI-2) will be described.
The compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in the formula (ZI) each independently represent an organic group having no aromatic ring. Here, the aromatic ring also 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 independently, preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group or 2-oxocyclo. It is an alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (for example, a methyl group or an ethyl group, etc.). Propyl group, butyl group, and pentyl group), and cycloalkyl group 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, 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 represented by the following general formula (ZI-3) and has a phenacylsulfonium salt structure.

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

Even if 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 are combined to form a ring structure, respectively. Often, this ring structure may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings in which two or more of these rings are combined. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

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.
As the group formed by bonding R _5c and R _6c , and R _5c and R _x , a single bond or an alkylene group is preferable. 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 the general formula (ZI-4),
l represents an integer from 0 to 2.
r represents an integer from 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 substituents.
R ₁₄ represents 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 group having a cycloalkyl group. These groups may have substituents. When a plurality of R ₁₄ are present, each independently represents the above group such as a hydroxyl group.
R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have substituents. Bonded to two R ₁₅ each other may form a ring. When two R ₁₅ are combined to form a ring together, in the ring skeleton may contain a hetero atom such as an oxygen atom, or a nitrogen atom. In one embodiment, two R ₁₅ is an alkylene group, it is preferable to form a ring structure.
Z ⁻ represents an anion.

In the general formula (ZI-4), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched chain. The alkyl group preferably has 1 to 10 carbon atoms. As the alkyl group, a methyl group, an ethyl group, an n-butyl group, a t-butyl group and the like are more preferable.

Next, the general formulas (ZII) and (ZIII) will be described.
In the general formulas (ZII) and (ZIII), R _{204 to} R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
As the aryl group of R _{204 to} R _207, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. 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.
Examples of the alkyl group and cycloalkyl group of R _{204 to} R ₂₀₇ include a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, etc.). Butyl group and pentyl group) or cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) are preferable.

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may each independently have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 to 15 carbon atoms). 15), aryl groups (for example, 6 to 15 carbon atoms), alkoxy groups (for example, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like can be mentioned.
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 represented anion is preferred.

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

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Further, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.
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 Xfs are fluorine atoms.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. If R ₄ and _{R 5} there are a plurality, _{R 4} and _{R 5} may each be the same or different.
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 hydrogen atoms.
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 the general formula (3).

L represents a divalent linking group. When there are a plurality of L's, the L's 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₋ , alkylene group (preferably 1 to 6 carbon atoms), cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene group (preferably 2 to 6 carbon atoms), and a combination thereof. Divalent linking groups and the like can be mentioned. 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 a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Of these, alicyclic groups 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, are 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 the diffusion of acid more. Further, the heterocyclic group may 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 non-aromatic heterocycle include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above-mentioned resin. As the heterocycle 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) and a cycloalkyl group (monocyclic, polycyclic, and spiroring). Any of them may be used, preferably 3 to 20 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group and a sulfonamide. Examples include groups and sulfonic acid ester groups. The carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be 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 preferable. Here, L, q and W are the same as in the general formula (3). q'represents an integer from 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 anions represented by the formula (4) are also preferable.

In general formula (4),
X ^B1 and X ^B2 each independently represent a monovalent organic group having no hydrogen atom or fluorine atom. It is preferable that X ^B1 and X ^B2 are hydrogen atoms.
X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. It is preferable that 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 monovalent organic groups having a fluorine atom or a fluorine atom. Is more preferable. It is even more preferred that both X ^B3 and X ^B4 are fluorine-substituted alkyl groups.
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, it is preferably a benzenesulfonic acid anion substituted with a branched chain alkyl group or a cycloalkyl group.

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) Aromatic sulfonic acid anion represented by is also preferable.

In formula (SA1),
Ar represents an aryl group and may further have a substituent other than the sulfonic acid anion and the − (DB) group. Further, examples of the substituent which may be possessed include a fluorine atom and a hydroxyl group.

n represents an integer of 0 or more. As n, 1 to 4 are preferable, 2 to 3 are more preferable, and 3 is further 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 of these.

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 the general formula (ZI) and the iodonium cation in the general formula (ZII) are shown below.

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

The above cations and anions can be arbitrarily combined and used as a photoacid generator.

The photoacid generator may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Further, the form of the low molecular weight compound and the form incorporated in a part of the polymer may be used in combination.
The photoacid generator is preferably in the form of a low molecular weight compound.
When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.
When the photoacid generator is in the form of being 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). ..
The photoacid generator may be used alone or in combination of two or more.
The content of the photoacid generator in the composition (the total of a plurality of types, if present) is preferably 0.1 to 35% by mass, preferably 0.5 to 25% by mass, based on the total solid content of the composition. Is more preferable, 3 to 20% by mass is further preferable, and 3 to 15% by mass is particularly preferable.
When the photoacid generator contains a compound represented by the above general formula (ZI-3) or (ZI-4), the content of the photoacid generator contained in the composition (if a plurality of types are present, the content thereof). The total) is preferably 5 to 35% by mass, more preferably 7 to 30% by 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 control agent (D). The acid diffusion control agent (D) acts as a quencher that traps the acid generated from the photoacid generator or the like during exposure and suppresses the reaction of the acid-degradable resin in the unexposed portion due to the excess generated acid. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation, an onium salt (DC) which is a weak acid relative to an acid generator, and a nitrogen atom. A low molecular weight compound (DD) having a group having a group desorbed by the action of an acid, an onium salt compound (DE) having a nitrogen atom in the cation portion, or the like can be used as an acid diffusion control agent. In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0995] to [0187] of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1. The known compounds disclosed in paragraphs [0403] to [0423] of the specification and paragraphs [0259] to [0328] of US 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 a structure represented by the following formulas (A) to (E) are preferable.

In the general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, respectively, independently of a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl. Represents a group (6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may be combined 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 groups in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
Regarding the above alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
It is more preferable that the alkyl groups in the general formulas (A) and (E) are unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidin, pyrazole, pyrazoline, piperazin, aminomorpholine, aminoalkylmorpholin, piperidine and the like are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, etc. More preferably, 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, or an aniline derivative having a hydroxyl group and / or an ether bond.

A basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation (hereinafter, also referred to as “compound (DB)”) has a proton acceptor functional group and is active light or It is a compound that is decomposed by irradiation with radiation to reduce or disappear its proton accepting property, or to change from proton accepting property to acidic.

A proton acceptor functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π-conjugated group. 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 shown in the following formula.

Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza crown ether structure, a 1-3-grade amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.

The compound (DB) is decomposed by irradiation with active light or radiation to reduce or eliminate the proton acceptor property, or generate a compound in which 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 acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group, and is specific. Means that when a proton adduct is formed from a compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
Proton acceptability can be confirmed by measuring pH.

The acid dissociation constant pKa of the compound generated by decomposing the compound (DB) by irradiation with active light or radiation preferably satisfies pKa <-1, more preferably -13 <pKa <-1. It is more preferable to satisfy 13 <pKa <-3.

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in, for example, Chemical Handbook (II) (Revised 4th Edition, 1993, edited by Japan Chemical Society, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be 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 Hammett's substituent constants and values based on a database of publicly known literature values. All pKa values described herein indicate values calculated using this software package.

Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labors).

In the composition of the present invention, an onium salt (DC), which is a weak acid relative to the photoacid generator, can be used as an acid diffusion control agent.
When a photoacid generator and an onium salt that generates an acid that is relatively weak to the acid generated from the photoacid generator are mixed and used, the photoacid generator is activated by active light or irradiation with radiation. When the acid generated from the above collides with an onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange to form an onium salt having a strong acid anion. In this process, the strong acid is exchanged for the weak acid having a lower catalytic ability, so that the acid is apparently inactivated and the acid diffusion can be controlled.

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

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

Preferred examples of the sulfonium cation or 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).

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

In the 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 that links the cation moiety and the anion moiety.
-X ^{- _is,} -COO ^{-, -SO} 3 - represents an anion portion selected from -R ₄ ^-, -SO ₂ -, and ^-N. R ₄ is a linking site with the adjacent N atom, a carbonyl group (-C (= O) -) , sulfonyl group _{(-S (= O) 2 -} ), and sulfinyl group (-S (= O) - ) Represents a monovalent substituent having at least one of them.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be combined with each other to form a ring structure. Further, in the general formula (C-3), two of R _{1 to} R ₃ are combined to represent one divalent substituent, which may be bonded to an N atom by a double bond.

Substituents 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. Examples thereof include a carbonyl group and an arylaminocarbonyl group. It is preferably an alkyl group, a cycloalkyl group, or an aryl group.

L ₁ as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and 2 of these. Examples include groups made up of a combination of seeds and above. 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 of these.

A low molecular weight compound (DD) having a nitrogen atom and having a group desorbed by the action of an acid (hereinafter, also referred to as “compound (DD)”) has a group desorbed by the action of an acid on the nitrogen atom. It is preferably an amine derivative having.
As the group desorbed by the action of the acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminol ether group is preferable, and a carbamate group or a hemiaminol ether group is more preferable. ..
The molecular weight of compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
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 the general formula (d-1)
Rb is independently 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), and an aralkyl group (preferably 3 to 30 carbon atoms). It preferably represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). 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 independently hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups, alkoxy groups, or It may be substituted with a halogen atom. The same applies to the alkoxyalkyl group indicated by Rb.

As Rb, a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
Examples of the ring formed by connecting the two Rbs to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
Specific structures of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph [0466] of US Patent Publication US2012 / 0135348A1.

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

In the 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, the two Ras may be the same or different, and the two Ras may be linked to each other to form a heterocycle with the nitrogen atom in the equation. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in the above general formula (d-1), and the same applies to preferred examples.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra are independently substituted with the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb, respectively. As a good group, it may be substituted with a group similar to the group described above.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra (these groups may be substituted with the above group) include groups similar to the above-mentioned specific examples for Rb. Be done.
Specific examples of a particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012/01335348A1.

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter, also referred to as “compound (DE)”) is preferably a compound having a basic moiety containing a nitrogen atom in the cation portion. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is more preferable that all the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-attracting functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly linked to the nitrogen atom.
Preferred specific examples of compound (DE) include, but are not limited to, the compounds disclosed in paragraph [0203] of US Patent Application Publication 2015/0309408A1.

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

In the composition of the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more.
The content of the acid diffusion control agent (D) in the composition (the total of a plurality of types, if present) is preferably 0.1 to 10% by mass, preferably 0.1 to 10% by mass, based on the total solid content of the composition. 5% by 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).
By including the hydrophobic resin (E) in the composition of the present invention, the static / dynamic contact angle on the surface of the sensitive light-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve development characteristics, suppress outgas, improve immersion liquid followability 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, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and a polar / non-polar substance is used. It does not have to contribute to uniform mixing.

The hydrophobic resin (E) is selected from the group consisting of "fluorine atoms", "silicon atoms", and "CH _three- part structure contained in the side chain portion of the resin" from the viewpoint of uneven distribution on the surface layer of the film. 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 the silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin, and the side chain may be contained. It may be contained in the chain.

When the hydrophobic resin (E) contains a fluorine atom, the partial structure having a fluorine atom 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. 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 alkaline developer and increases its solubility in an alkaline developer (hereinafter, also referred to as a polarity converting group).
(Z) Group decomposed by the action of 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, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (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) ) Methylene group and the like can be mentioned.
As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis (alkylcarbonyl) methylene group is preferable.

Examples of the group (y) that decomposes due to the action of the alkaline developing solution and increases the solubility in the alkaline developing solution include a lactone group, a carboxylic acid ester group (-COO-), and an acid anhydride group (-C (O) OC). (O)-), acidimide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate ester group (-OC (O) O-), sulfate ester 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.
Examples of the repeating unit containing these groups include repeating units in which these groups are directly bonded to the main chain of the resin, and examples thereof include repeating units made of acrylic acid ester and methacrylic acid ester. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced into the end of the resin by using a polymerization initiator or chain transfer agent having these groups at the time of polymerization.
Examples of the repeating unit having a lactone group include the same repeating units having a lactone structure described above in the section of resin (A).

The content of the repeating unit having a group (y) that decomposes by the action of the alkaline developer and increases the solubility in the alkaline developer is 1 to 100 mol% with respect to all the repeating units in the hydrophobic resin (E). Is preferable, 3 to 98 mol% is more preferable, and 5 to 95 mol% is further preferable.

In the hydrophobic resin (E), the repeating unit having a group (z) that decomposes by the action of an acid may be the same as the repeating unit having an acid-degradable group mentioned in the resin (A). The repeating unit having a group (z) decomposed 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 the group (z) decomposed by the action of the acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all the repeating units in the hydrophobic resin (E). 20 to 60 mol% is more preferable.
The hydrophobic resin (E) may further have a repeating unit different from the repeating unit described above.

The repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all the repeating units in the hydrophobic resin (E). The repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on all the repeating units in the hydrophobic resin (E).

On the other hand, especially if the hydrophobic resin (E) comprises a CH ₃ partial structure side chain moiety, a hydrophobic resin (E) is also preferable that is substantially free of fluorine atom and a silicon atom. Further, it is preferable that the hydrophobic resin (E) is substantially composed of only repeating units composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

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

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

As the hydrophobic resin (E), a known resin can be appropriately selected and used alone or as a mixture thereof. For example, known resins disclosed in paragraphs [0451]-[0704] of U.S. Patent Application Publication 2015/016830A1 and paragraphs [0340]-[0356] of U.S. Patent Application Publication 2016/0274458A1. Can be suitably used as the hydrophobic resin (E). Further, the repeating unit disclosed in paragraphs [0177] to [0258] of US Patent Application Publication No. 2016/0237190A1 is also preferable as the repeating unit constituting the hydrophobic resin (E).

A preferred example of the monomer corresponding to the repeating unit constituting the hydrophobic resin (E) is shown below.

The hydrophobic resin (E) may be used alone or in combination of two or more.
It is preferable to mix and use two or more kinds of hydrophobic resins (E) having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure.
The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention.

<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 U.S. Patent Application Publication No. 2016/0070167A1, paragraphs [0210] to [0235] of U.S. Patent Application Publication No. 2015/0004544A1, U.S. Patent Application Publication No. 2016/0237190A1. Known solvents disclosed in paragraphs [0424] to [0426] of the specification and paragraphs [0357] to [0366] of the US Patent Application Publication No. 2016/0274458A1 can be preferably used.
Examples of the solvent that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionate, and cyclic lactone (preferably having 4 to 10 carbon atoms). Examples thereof include organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used may be used.
As the solvent having a hydroxyl group and the solvent having no hydroxyl group, the above-mentioned exemplified compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether (propylene glycol monomethyl ether). PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. Further, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene Glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, Cyclohexanone, cyclopentanone or 2-heptanone are more preferred. Propylene carbonate is also preferable as the solvent having no hydroxyl group.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 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, and may be a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

<Crosslinking agent (G)>
The composition of the present invention may contain a compound (hereinafter, also referred to as a cross-linking agent (G)) that cross-links the resin by the action of an acid. As the cross-linking agent (G), a known compound can be appropriately used. For example, known compounds disclosed in paragraphs [0379]-[0431] of U.S. Patent Application Publication 2016 / 0147154A1 and paragraphs [0064]-[0141] of U.S. Patent Application Publication 2016/0282720A1. Can be suitably used as the cross-linking agent (G).
The cross-linking agent (G) is a compound having a cross-linking group capable of cross-linking the resin, and examples of the cross-linking group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, and an oxylan ring. And the oxetane ring and the like.
The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxylan ring or an oxetane ring.
The cross-linking agent (G) is preferably a compound (including a resin) having two or more cross-linking groups.
The cross-linking agent (G) is more preferably a phenol derivative, a urea-based compound (compound having a urea structure) or a melamine-based compound (compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.
The cross-linking agent may be used alone or in combination of two or more.
The content of the cross-linking agent (G) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, still more preferably 5 to 30% by mass, based on the total solid content of the resist composition.

<Surfactant (H)>
The composition of the present invention may contain a surfactant. When a surfactant is contained, a fluorine-based and / or a 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 preferable.

When the composition of the present invention contains a surfactant, a pattern having good sensitivity and resolution and few adhesions and development defects can be obtained when an exposure light source of 250 nm or less, particularly 220 nm or less is used.
Fluorine-based and / or silicon-based surfactants include those described in paragraph [0276] of U.S. Patent Application Publication No. 2008/0248425.
In addition, other surfactants other than the 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 the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. preferable.
On the other hand, when the content of the surfactant is 10 ppm or more with respect to the total solid content of the composition, the uneven distribution of the surface of the hydrophobic resin (E) is increased. As a result, the surface of the sensitive light-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability during immersion exposure is improved.

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

<Preparation method>
The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and even more preferably 2.0 to 5.3% by mass. The solid content concentration is the 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 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 the resolving power. 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 coatability or film forming property.

The composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering the mixture, and then coating the composition 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, still more preferably 0.03 μm or less. The 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 arranged in series or in parallel. It may be connected to and filtered. Moreover, the composition may be filtered a plurality of times. Further, the composition may be degassed before and after the filter filtration.

<Use>
The composition of the present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition whose properties change in response to irradiation with active light or radiation. More specifically, the composition of the present invention is used in a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board such as a liquid crystal or a thermal head, a molding structure for imprinting, another photofabrication step, or a photofabrication step. The present invention relates to a lithographic printing plate or a radiation-sensitive or radiation-sensitive resin composition used for producing an acid-curable composition. The pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, a MEMS (Micro Electro Mechanical Systems), and the like.

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

The pattern forming method of the present invention
(I) A step of forming a resist film (actinic cheilitis or radiation-sensitive film) on a support by the above-mentioned actinic cheilitis or radiation-sensitive resin composition (resist film forming step).
(Ii) A step (exposure step) of exposing the resist film (irradiating active light rays or radiation), and
(Iii) A step of developing the exposed resist film with a developing solution (development step).
Have.

The pattern forming method of the present invention is not particularly limited as long as it includes the above steps (i) to (iii), and may further include the following steps.
In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be immersion exposure.
The pattern forming method of the present invention preferably includes (iv) preheating (PB: PreBake) step before the (ii) exposure step.
The pattern forming method of the present invention preferably includes (v) post-exposure heating (PEB: Post Exposure Bake) step after the (ii) exposure step and before the (iii) development step.
The pattern forming method of the present invention may include (ii) exposure steps 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-mentioned (i) film forming step, (ii) exposure step, and (iii) developing step can be performed by a generally known method.
Further, 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, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/02444438 and International Patent Application Publication No. 2016/157988A can be preferably used. The composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent.
A protective film may be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.

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

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

The wavelength of the light source used in the exposure process is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, polar ultraviolet light (EUV), X-ray, and electron beam. Among these, far-ultraviolet light is preferable, and the wavelength thereof 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), or an electron beam or the like, KrF excimer laser, ArF excimer laser, EUV or electron beam is preferable.

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

As the alkaline developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but in addition to this, alkaline aqueous solutions such as inorganic alkali, 1st to 3rd amine, alcohol amine, and cyclic amine are also used. It can be used.
Further, the alkaline developer may contain an appropriate amount of alcohols and / or a surfactant. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15.
The time for developing with an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkaline 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 a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. Is preferable.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone (methylamylketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutylketone. Cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate and the like can be mentioned.

Examples of the ester solvent 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, and 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 Butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, butyl propionate and the like can be mentioned.

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 developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. % Is particularly preferable.

The organic developer may contain an appropriate amount of a known surfactant, if necessary.

The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the developing solution.

The organic developer may contain the acid diffusion control agent described above.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method), and a substrate. Examples include a method of spraying the developer on the surface (spray method) or a method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic discharge method). Be done.

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

(Iii) It is preferable to include a step of washing with a rinsing solution (rinsing step) after the developing step.

For example, pure water can be used as the rinsing solution used in the rinsing step after the developing step using the alkaline developer. Pure water may contain an appropriate amount of a surfactant. In this case, after the developing step or the rinsing step, a process of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be added. Further, after the rinsing treatment or the treatment with the supercritical fluid, a heat treatment may be performed to remove the water remaining in the pattern.

The rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a general solution containing an organic solvent can be used. As the rinsing solution, use a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. Is preferable.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent include the same as those described for the developing solution containing the organic solvent.
As the rinsing solution used in the rinsing step in this case, a rinsing solution containing a monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the rinsing step include linear, branched, and 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 methylisobutylcarbinol can be mentioned. Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, methylisobutylcarbinol and the like. ..

A plurality of each component may be mixed, or may be mixed and used with an organic solvent other than the above.
The water content in the rinse solution is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. Good development characteristics can be obtained by setting the water content to 10% by mass or less.

The rinse solution may contain an appropriate amount of a surfactant.
In the rinsing step, the substrate developed with an organic developer is washed with a rinsing solution containing an organic solvent. The cleaning treatment method is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method of spraying a rinse liquid on the substrate surface (spray method). Above all, it is preferable to perform the cleaning treatment by the rotary coating method, and after cleaning, rotate the substrate at a rotation speed of 2,000 to 4,000 rpm to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. This heating step removes the developer and rinse liquid remaining between and inside the patterns. In the heating step after the rinsing step, the heating temperature is usually 40 to 160 ° C., preferably 70 to 95 ° C., and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The sensitive light-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 developing solution, a rinsing solution, an antireflection film forming composition, or The composition for forming a top coat, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt or less, further preferably 10 ppt or less, and substantially not contained (below the detection limit of the measuring device). Is particularly preferable.

Examples of the method for removing impurities such as metals from the above-mentioned various materials include filtration using a filter. The filter pore size is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step. The filter preferably has a reduced amount of eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426).
In addition to filter filtration, impurities may be removed by an adsorbent, and filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and 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. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500).
Further, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. Alternatively, a method such as lining the inside of the apparatus with Teflon (registered trademark) to perform distillation under conditions in which contamination is suppressed as much as possible can be mentioned. The preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.

The above-mentioned various materials are described in US 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 with impurities. It is preferable to store it in a 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 treating the pattern with a plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957 can be mentioned. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. A known method as described in 8328 83280N-1 “EUV Resist Curing Technology for LWR Reduction and Etch Sensitivity Enhancement” may be applied.
Further, the pattern formed by the above method is a spacer process disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Application Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/0209941. Can be used as a core material (Core) of.

[Manufacturing method of electronic device]
The present invention also relates to a method for manufacturing an electronic device, including the above-mentioned pattern forming method. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electrical and electronic device (for example, home appliances, OA (Office Automation) related devices, media related devices, optical devices, communication devices, etc.). Will be done.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not construed as limiting by the examples shown below.

<Synthesis Example 1: Synthesis of compound MA-1>
The outline of the procedure for synthesizing compound MA-1 in the examples is shown below.

(Synthesis of compound (i))
416 mL of a THF solution containing 20% by mass of LDA (lithium diisopropylamide) was added to 350 ml of dehydrated THF (tetrahydrofran), and the obtained 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. Then, the obtained solution was stirred at 25 ° C. for 2 hours under a nitrogen atmosphere. After stopping the reaction by adding 300 g of water to this solution, the organic phase was washed with 400 g of water 5 times. The obtained concentrated solution 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. Then, the solution was stirred at 25 ° C. for 1 hour under a nitrogen atmosphere. Next, a solution obtained by further dissolving 60 g of compound (i) in 411 ml of dehydrated THF was added dropwise to the obtained solution. The obtained solution was stirred at 25 ° C. for 1 hour under a nitrogen atmosphere, and then 400 g of an aqueous ammonium chloride 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 (1.6 M) was added dropwise to this solution, and the solution was stirred for 1 hour. Then, 27 g of methacrylic acid chloride was added dropwise to the obtained solution, and the solution was stirred at 25 ° C. for 2 hours under a nitrogen atmosphere. After stopping the reaction by adding 400 g of water to this solution, the organic phase was washed 5 times with 400 g of water. The obtained concentrate 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 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 the polymerization initiator V-601 (Wako Pure Chemical Industries, Ltd.) based on the total amount of these monomers. Co., Ltd.) was dissolved in 36 g of cyclohexanone to obtain a solution.
This solution was then added dropwise to the three-necked flask over 4 hours. After completion of the dropping, the reaction was further carried out at 85 ° C. for 2 hours. The reaction mixture was allowed to cool, diluted with 40 g of cyclohexanone, and the diluted solution was added dropwise to a mixture 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.

In the same manner, the other resins (A-2) to (A-15) shown below were synthesized.

The structure of the monomer used in the synthesis of the resin (A) used in Examples and Comparative Examples is shown below. In addition, Table 1 below shows the molar ratio of the repeating unit, the weight average molecular weight (Mw), and the dispersity (Mw / Mn) of each resin. Further, the combination of the repeating units of each of the resins (A-1) to (A-15) 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 control agent (D) used in Examples and Comparative Examples is shown below.

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

The solvent (F) used in Examples and Comparative Examples 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 Cheilitis or Radiation Sensitive Resin Composition>
Each component shown in Table 3 below was mixed so as to have a solid content concentration of 4% by mass to prepare an actinic cheilitis or radiation-sensitive resin composition (hereinafter, also referred to as a resin composition). The solid content here means all components other than the solvent (F). The mixture was blended so that the solid content had a ratio according to the parts by mass shown in Table 3. The resin composition was first filtered with a polyethylene filter having a pore diameter of 50 nm, then with a nylon filter having a pore diameter of 10 nm, and finally with a polyethylene filter having a pore diameter 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>
The organic antireflection film forming composition ARC29SR (manufactured by Brewer Science) is applied onto the silicon wafer, and the silicon wafer coated with the organic antireflection film forming composition is baked at 205 ° C. for 60 seconds to obtain a film thickness of 98 nm. Antireflection film was formed. The resin compositions of Examples and Comparative Examples shown in Table 3 are applied thereto and baked at 100 ° C. for 60 seconds to form an actinic or radiation-sensitive film (resist film) having a film thickness of 90 nm. did.
A line was applied to the obtained resist film using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.730, inner sigma 0.630, XY deflection). Exposure was performed through a 6% halftone mask with a 1: 1 line and space pattern with a width of 75 nm. Ultrapure water was used as the immersion liquid.
The resist film after exposure 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. Then, 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 with slagness (LWR, nm)]
When observing a resolved 75 nm (1: 1) line-and-space pattern from above the pattern using a length-measuring scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)), lines 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 is, and the better the performance is.

From Table 4, examples using the sensitive light-sensitive or radiation-sensitive resin composition containing a resin having a repeating unit having a group represented by the general formula (1) are represented by the general formula (1). It was confirmed that the LWR was good as compared with the comparative example using the sensitive light-sensitive or radiation-sensitive resin composition containing a resin having a group and no repeating unit.
From the comparison between Example 10 and Example 11, it was confirmed that when X in the general formula (2) was a single bond (Example 10), a better LWR was exhibited.
From the comparison of Examples 1, 2 and 9, it was confirmed that the cyclic structure formed by Z of 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 even when the resist film formed in the above example was subjected to ArF exposure and the film after exposure was subjected to alkaline development, a good pattern of LWR could be obtained. Similarly, even when the resist film formed in the above example is subjected to KrF exposure, electron beam exposure or EUV exposure, and the film after exposure is subjected to alkali development or organic solvent development. It was confirmed that LWR could obtain a good pattern.

Claims (10)

A sensitive light-sensitive or radiation-sensitive resin composition containing a resin having a repeating unit having a group represented by the following general formula (1).
In the general formula (1), R ₁ represents a chain alkyl group having 3 or more carbon atoms. R ₂ and R ₃ each independently represent a chain alkyl group. Here, the total number of carbon atoms contained in R ₁ , R ₂ and R ₃ is 5 to 6. Z represents a group that forms a monocyclic or polycyclic cyclic structure with a carbon atom. * Represents the bond position. The actinic 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 the 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 the general formula (1). Including a resin having a repeating unit having a group represented by the following general formula (1).
A sensitive light-sensitive or radiation-sensitive resin composition in which the content of the repeating unit having a group represented by the general formula (1) is 55 to 90 mol% with respect to all the repeating units in the resin. ..
In the general formula (1), R ₁ represents a chain alkyl group. R ₂ and R ₃ each independently represent a chain alkyl group having 1 carbon atom. 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 alicyclic structure with a carbon atom. * Represents the bond position. The actinic or radiation-sensitive resin composition according to claim 3, wherein the repeating unit is a repeating unit represented by the following general formula (2).
In the 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 the general formula (1). The actinic or radiation-sensitive resin composition according to claim 2 or 4, wherein X is a single bond. The actinic or radiation-sensitive resin composition according to any one of claims 1 to 5 , wherein Z is a group that forms a monocyclic alicyclic structure together with a carbon atom. The alicyclic structure is a alicyclic structure 5 or 6 carbon atoms, sensitive or radiation-sensitive resin composition according to claim 6. A resist film formed of the actinic or radiation-sensitive resin composition according to any one of claims 1 to 7 . A resist film forming step of forming a resist film using the actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7 .
An exposure step for exposing the resist film and
A pattern forming method including a developing step of developing the exposed resist film with a developing solution. A method for manufacturing an electronic device, including the pattern forming method according to claim 9 .