WO2019167451A1

WO2019167451A1 - Actinic-ray-sensitive or radiation-sensitive resin composition, actinic-ray-sensitive or radiation-sensitive film, pattern formation method, and electronic device production method

Info

Publication number: WO2019167451A1
Application number: PCT/JP2019/000914
Authority: WO
Inventors: 暁 ▲高▼田; 修平山口; 敦靖野崎
Original assignee: 富士フイルム株式会社
Priority date: 2018-02-28
Filing date: 2019-01-15
Publication date: 2019-09-06
Also published as: JP7125470B2; TW201936671A; JPWO2019167451A1; TWI782174B

Abstract

Provided are: an actinic-ray-sensitive or radiation-sensitive resin composition which, even when the exposure scan rate is ultra high (e.g., 700 mm/sec or higher), exhibits high immersion liquid follow-up performance for an exposure device, and can reduce both liquid immersion defects and development defects; and an actinic-ray-sensitive or radiation-sensitive film, a pattern formation method, and an electronic device production method using the same. This actinic-ray-sensitive or radiation-sensitive resin composition contains a resin (P) having a repeating unit represented by the general formula (1) and a resin (A) having a group that is decomposed and that increases the polarity due to an acid acting thereupon. In the general formula (1), Z represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R₁₁OCH₂-, or a group represented by R₁₂OC(=O)CH₂-. R₁₁ and R₁₂ independently represent a monovalent substituent. X represents an oxygen atom or a sulfur atom. L represents a single bond or an (m + 1)-valent linking group. R represents a specific group. m represents a positive integer. When m is 2 or more, the multiple Rs may be the same or different from one another. When L represents a single bond, m represents 1.

Description

Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern formation method, and electronic device manufacturing method

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

Since the resist for KrF excimer laser (248 nm), a pattern formation method using chemical amplification has been used to compensate for the sensitivity reduction due to light absorption. For example, in the positive chemical amplification method, first, a photoacid generator contained in an exposed portion is decomposed by light irradiation to generate an acid. Then, in the post-exposure baking (PEB: Post Exposure Bake) process or the like, the alkali-insoluble group contained in the photosensitive composition is changed to an alkali-soluble group by the catalytic action of the generated acid. Thereafter, development is performed using, for example, an alkaline solution. Thereby, an exposed part is removed and a desired pattern is obtained.
In the above method, various alkali developers have been proposed. For example, as this alkaline developer, a 2.38 mass% TMAH (tetramethylammonium hydroxide aqueous solution) aqueous alkaline developer is generally used.

To reduce the size of semiconductor elements, the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA). Currently, an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. ing. As a technique for further increasing the resolving power, a method (that is, an immersion method) that fills a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) between the projection lens and the sample has been proposed (for example, a patent). References 1-2).

JP 2011-2805 A JP 2012-242800 A

In recent years, along with demands for improving the productivity of various electronic devices, it has been required to form an intended resist pattern in a shorter time even in the formation of a resist pattern.
As one of the methods to shorten the resist pattern formation time, it is required to improve the scanning speed in the exposure process using the immersion exposure apparatus. In addition, it is very difficult to suppress various defects while having high followability of the immersion liquid with respect to the exposure apparatus.
Therefore, the present invention reduces both immersion defects and development defects while having a high followability of the immersion liquid to the exposure apparatus even if the scanning speed of the exposure is set to an extremely high speed (for example, 700 mm / second or more). It is an object to provide a possible actinic ray-sensitive or radiation-sensitive resin composition, and an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and an electronic device manufacturing method using the same. .

As a result of intensive studies by the present inventors, there is a demand for a material that adapts to the high followability of the immersion liquid with respect to the exposure apparatus when the exposure scanning speed is extremely high in the exposure process using the immersion exposure apparatus. It was found that the hydrophobicity of the material is related to the above performance.
The present inventors paid attention to this point and, in the actinic ray-sensitive or radiation-sensitive resin composition, adopted a resin having a specific terminal structure as a hydrophobic resin. The present invention has been completed by finding that both immersion defects and development defects can be further reduced while maintaining a high followability of the immersion liquid with respect to the exposure apparatus even at ultra high speed (for example, 700 mm / second or more). It is.
That is, the present inventors have found that the above problem can be solved by the following configuration.

[1]
Actinic ray-sensitive or radiation-sensitive resin containing a resin (P) having a repeating unit represented by the following general formula (1), and a resin (A) having a group that is decomposed by the action of an acid to increase polarity Composition.

In the general formula (1), Z represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R ₁₁ OCH ₂ —, or a group represented by R ₁₂ OC (═O) CH ₂ —. Represents. R ₁₁ and R ₁₂ each independently represents a monovalent substituent.
X represents an oxygen atom or a sulfur atom.
L represents a single bond or a (m + 1) -valent linking group.
R represents a group represented by the following formula (1-1).
m represents a positive integer. When m is 2 or more, the plurality of R may be the same as or different from each other. When L represents a single bond, m represents 1.

In the above formula (1-1),
* Represents a bond with L or X.
R ₁ and R ₁ ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.

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

In the general formula (2), Z ₂ is represented by a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R ₂₁ OCH ₂ —, or R ₂₂ OC (═O) CH ₂ —. Represents a group. R ₂₁ and R ₂₂ each independently represents a monovalent substituent.
X ₂ represents an oxygen atom or a sulfur atom.
R ₂ represents a group represented by the following formula (1-1).

In the above formula (1-1),
* Represents a bond to X _2.
R ₁ and R ₁ ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.

[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (3) or (4): .

In the general formula (3), _{Z 3} is a hydrogen atom, an alkyl group, an alkoxy group, a halogen _atom, R 31 OCH ₂ - represented by -, a group represented by or _{R 32 OC (= O) CH} 2 Represents a group. R ₃₁ and R ₃₂ each independently represents a monovalent substituent.
X ₃ represents an oxygen atom or a sulfur atom.
L ₃ represents a divalent linking group.
R ₃ represents a group represented by the following formula (1-1).
In the general formula (4), Z ₄ represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.
X ₄ represents an oxygen atom or a sulfur atom.
L ₄ represents a divalent linking group.
R ₄ represents a group represented by the following formula (1-1).

In the above formula (1-1),
* Represents a bond with —C (═O) — or —O—.
R ₁ and R ₁ ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.

[4]
[1] to [3], wherein the resin (P) further has a repeating unit (a1) having an organic group having one or more CH ₃ partial structures which is stable to an acid in a side chain portion. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.

[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to [4], wherein the repeating unit (a1) is a repeating unit represented by the following general formula (5).

In the general formula (5), Za represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
Ra represents an alkyl group or a cycloalkyl group having one or more CH ₃ partial structures and stable to an acid.

[6]
Any one of [1] to [5], wherein the resin (P) further has a repeating unit (a2) having a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer. The actinic ray-sensitive or radiation-sensitive resin composition described.

[7]
The actinic ray-sensitive or radiation-sensitive resin composition according to [6], wherein the repeating unit (a2) is a repeating unit represented by the following general formula (6) or (7).

In the general formula (6), Zb represents a hydrogen atom, an alkyl group, a halogen atom, a group represented by R ₆₁ OCH ₂ —, or a group represented by R ₆₂ OC (═O) CH ₂ —. R ₆₁ and R ₆₂ each independently represent a monovalent substituent.
Rd represents an electron withdrawing group.
In the general formula (7), Zc represents a hydrogen atom, a halogen atom, or an alkyl group.
L ₁ represents an alkylene group, a cycloalkylene group, or a group formed by combining these. If L ₁ is present in plurality, a plurality of L ₁ may be be the same or different from each other.
Re represents a divalent linking group. When a plurality of Re are present, the plurality of Re may be the same as or different from each other.
n1 represents an integer of 0 to 5.
Xa represents an alkylene group, an oxygen atom, or a sulfur atom.
Rf represents an electron withdrawing group.
m1 represents an integer of 1 to 3.

[8]
An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7].

[9]
(I) a step of forming an actinic ray-sensitive or radiation-sensitive film with the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7],
(Ii) irradiating the actinic ray-sensitive or radiation-sensitive film with an actinic ray or radiation; and
(Iii) A pattern forming method including a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation with a developer.

[10]
The pattern forming method according to [9], wherein the developer is an alkali developer.

[11]
The manufacturing method of an electronic device containing the pattern formation method as described in [9] or [10].

According to the present invention, even when the scanning speed of exposure is set to an ultra-high speed (for example, 700 mm / second or more), both immersion defects and development defects are reduced while having high followability of the immersion liquid to the exposure apparatus. A possible actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film using the same, a pattern forming method, and a method for producing an electronic device can be provided.

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

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

[Actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention will be described.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a resist composition, which may be a positive resist composition or a negative resist composition. The resist composition is preferably a mold type resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development, but is preferably a resist composition for alkali development.
The resist composition of the present invention is typically a chemically amplified resist composition.
Hereinafter, components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) will be described in detail.

<Resin (P)>
The composition of this invention contains resin (P) which has a repeating unit represented by following General formula (1).

The resin (P) is preferably a hydrophobic resin. In addition, it is preferable that hydrophobic resin (P) is resin different from resin (A).
The resin (P) is preferably designed to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive film.

As described above, the repeating unit represented by the general formula (1) of the present invention has a group represented by the general formula (1-1).
For example, a group represented by the following formula (a) (* represents a bond) is known, but the structure represented by the following formula (a) is not sufficient to impart hydrophobicity. When the scanning speed is extremely high, high followability of the immersion liquid with respect to the exposure apparatus tends not to be ensured.

In order to improve the high followability of the immersion liquid with respect to the exposure apparatus when the scanning speed is extremely high, it is conceivable to improve the hydrophobicity of the resin, and the group represented by the following formula (b) (* A structure in which the hydrogen atom of the group represented by the above formula (a) is replaced with a carbon atom is also conceivable.

In order to improve the hydrophobicity of the resin including the structure in which the hydrogen atom of the group represented by the formula (a) is replaced with a carbon atom as described above, the immersion in the exposure apparatus when the scanning speed is extremely high Although the followability of the liquid is increased, the affinity for the alkaline developer is decreased on the contrary, so that development defects tend to be deteriorated. As described above, it has been extremely difficult to satisfy both the high followability of the exposure apparatus to the immersion liquid and the improvement of development defects when the scanning speed is set to be extremely high.
However, the present inventors have now made the actinic ray-sensitive or radiation-sensitive composition contain a resin (P) having a repeating unit represented by the general formula (1) as a hydrophobic resin. It has been found that even when the exposure scanning speed is set to an ultra-high speed (for example, 700 mm / second or more), both immersion defects and development defects can be further reduced while having high followability of the immersion liquid to the exposure apparatus.
This is because the group represented by the general formula (1-1) in the repeating unit represented by the general formula (1) gives an appropriate hydrophobic property to the resin (P), thereby making the exposure scan speed extremely high. In this case, the following ability of the immersion liquid to the exposure apparatus is sufficient, and the occurrence of immersion defects can be reduced while the affinity of the resin (P) to the alkaline developer can be sufficiently provided. This is thought to be because the occurrence of development defects was also reduced.

Examples of the alkyl group for Z include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group). A methyl group is preferred.
Examples of the alkoxy group for Z include an alkoxy group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms is preferable.
As a halogen atom of Z, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, for example, A fluorine atom or a chlorine atom is preferable.

The monovalent organic group as R ₁₁ and R ₁₂ is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 4 carbon atoms), a cycloalkyl group (preferably having 6 to 10 carbon atoms), and aryl. And a group (preferably having a carbon number of 6 to 10). The monovalent substituent as R ₁₁ and R ₁₂ may further have a substituent. Examples of such a further substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom. An atom, a hydroxyl group, an alkoxy group (preferably having 1 to 4 carbon atoms), a carboxy group, and the like can be given.
Z is preferably a hydrogen atom, an alkyl group or a halogen atom, more preferably a hydrogen atom, a methyl group or a fluorine atom, and even more preferably a hydrogen atom or a methyl group.
The alkyl group and alkoxy group as Z may further have a substituent. Examples of such a further substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, and an alkoxy group. (Preferably having 1 to 4 carbon atoms) and a carboxy group.
X represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

The (m + 1) -valent linking group as L is preferably a divalent or trivalent linking group (in other words, m is preferably 1 or 2) and is a divalent linking group. Is more preferable (in other words, m is preferably 1). The linking group as L is preferably a group consisting of an aliphatic group, an aromatic group, —O—, —C (═O) —, —S—, or a combination of two or more thereof.
For example, when m is 1 and the linking group as L is a divalent linking group, examples of the divalent aliphatic group include an alkylene group, an alkenylene group, an alkynylene group, or a polyalkyleneoxy group. Can do. Of these, an alkylene group and an alkenylene group are preferable, and an alkylene group is more preferable. The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The divalent aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group. Group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group, diarylamino group and the like. Examples of the divalent aromatic group include an aryl group. Of these, a phenylene group and a naphthylene group are preferable. The divalent aromatic group may have a substituent, and examples thereof include an alkyl group in addition to the examples of the substituent in the divalent aliphatic group.
When m is 2 or more, specific examples of the (m + 1) -valent linking group include groups obtained by removing any (m-1) hydrogen atoms from the specific examples of the divalent linking group described above. Can be mentioned.

Specific examples of L include, for example, the following linking groups, but are not limited thereto.

* Represents a bond with X, and r represents a bond with R.

In addition, as described above, these linking groups may further have a substituent.

Examples of the alkyl group for R ₁ and R ₁ ′ include, for example, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and Pentyl group), and an alkyl group having 1 to 5 carbon atoms is preferable.
Examples of the cycloalkyl group represented by R ₁ and R ₁ ′ include cycloalkyl groups having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group). A cycloalkyl group having 5 to 10 carbon atoms is preferred.
Examples of the aryl group for R ₁ and R ₁ ′ include an aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 10 carbon atoms (for example, a phenyl group or a naphthyl group) is preferable.

Each group of R ₁ and R ₁ ′ may further have a substituent. Examples of the substituent include a group having a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom (for example, an alkoxy group, an acyl group, etc. ), A group having a nitrogen atom (for example, an amino group, an alkylamino group, a dialkylamino group, etc.), and a fluorine atom and a chlorine atom are more preferable.

Preferred embodiments of R ₁ and R ₁ ′ include a fluorinated alkyl group in which a hydrogen atom of the above alkyl group is substituted with a fluorine atom, and a fluorinated aryl group in which a hydrogen atom of the above aryl group is substituted with a fluorine atom. Can be mentioned. Substitution with a fluorine atom may be for all hydrogen atoms or for some hydrogen atoms.

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

Specific examples and preferred examples of the alkyl group, alkoxy group and halogen atom of Z ₂ are the same as those described for the alkyl group, alkoxy group and halogen atom as Z in formula (1).
Specific examples and preferred examples of R ₂₁ and R ₂₂ include a group represented by R ₁₁ OCH ₂ — as Z in the general formula (1), or a group represented by R ₁₂ OC (═O) CH ₂ —. Are the same as those described for R ₁₁ and R ₁₂ .
Z ₂ is preferably a hydrogen atom, an alkyl group or a halogen atom, more preferably a hydrogen atom, a methyl group or a fluorine atom, still more preferably a hydrogen atom or a methyl group.
X ₂ is preferably an oxygen atom.
Specific examples and preferred examples of R ₂ are the same as those described for R in the general formula (1).

The repeating unit represented by the general formula (1) is preferably a repeating unit represented by the following general formula (3) or (4).
In addition, —CR bonded to the oxygen atom in the side chain of the repeating unit represented by the general formula (3) or —C (═O) — in the side chain of the repeating unit represented by the following general formula (4) _{Since 1} R ₁ ′ F is away from the main chain, the alkali developer tends to become familiar and the alkali reactivity of the ester moiety tends to increase. This is preferable because development defects tend to be further improved.
Further, from the viewpoint of high followability of the immersion liquid with respect to the exposure apparatus and suppression of development defects, the repeating unit represented by the general formula (3) is more preferable.

In the general formula (3), Z ₃ is represented by a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, a group represented by R ₃₁ OCH ₂ —, or R ₃₂ OC (═O) CH ₂ —. Represents a group. R ₃₁ and R ₃₂ each independently represents a monovalent substituent.
X ₃ represents an oxygen atom or a sulfur atom.
L ₃ represents a divalent linking group.
R ₃ represents a group represented by the following formula (1-1).
In the general formula (4), Z ₄ is represented by a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R ₄₁ OCH ₂ —, or R ₄₂ OC (═O) CH ₂ —. Represents a group. R ₄₁ and R ₄₂ each independently represents a monovalent substituent.
X ₄ represents an oxygen atom or a sulfur atom.
L ₄ represents a divalent linking group.
R ₄ represents a group represented by the following formula (1-1).

Specific examples and preferred examples of the alkyl group, alkoxy group and halogen atom of Z ₃ are the same as those described for the alkyl group, alkoxy group and halogen atom as Z in formula (1).
Specific examples and preferred examples of R ₃₁ and R ₃₂ include a group represented by R ₁₁ OCH ₂ — as Z in the general formula (1), or a group represented by R ₁₂ OC (═O) CH ₂ —. Are the same as those described for R ₁₁ and R ₁₂ .
Z ₃ is preferably a hydrogen atom, an alkyl group, or a halogen atom, more preferably a hydrogen atom, a methyl group, or a fluorine atom, and still more preferably a hydrogen atom or a methyl group.
X ₃ is preferably an oxygen atom.
Specific examples and preferred examples of the divalent linking group as L ₃ are the same as those described in L as the divalent linking group of the general formula (1).
In the general formula (3), L ₃ and R ₃ are not bonded to each other to form a ring.

Specific examples and preferred examples of the alkyl group, alkoxy group and halogen atom of Z ₄ are the same as those described for the alkyl group, alkoxy group and halogen atom as Z in formula (1).
Specific examples and preferred examples of R ₄₁ and R ₄₂ include a group represented by R ₁₁ OCH ₂ — as Z in the general formula (1), or a group represented by R ₁₂ OC (═O) CH ₂ —. Are the same as those described for R ₁₁ and R ₁₂ .
Z ₄ is preferably a hydrogen atom, an alkyl group or a halogen atom, more preferably a hydrogen atom, a methyl group or a fluorine atom, and even more preferably a hydrogen atom or a methyl group.
X ₄ is preferably an oxygen atom.
Specific examples and preferred examples of the divalent linking group as L ₄ are the same as those described in L as the divalent linking group of the general formula (1).
In the general formula (4), L ₄ and R ₄ are not bonded to each other to form a ring.

The content of the repeating unit represented by the general formula (1) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, based on all repeating units in the resin (P). 40 to 100 mol% is most preferable.

When the resin (P) has the repeating unit represented by the general formula (1) and other repeating units, the content of the repeating unit represented by the general formula (1) is the total content of the resin (P). It is preferably 10 to 90 mol%, more preferably 20 to 90 mol%, still more preferably 30 to 85 mol%, most preferably 40 to 85 mol%, based on the repeating unit.

Specific examples of the repeating unit represented by the general formula (1) are shown below, but the present invention is not limited to these. In the formula, X represents a halogen atom, and Ph represents a phenyl group.

The resin (P) preferably has a repeating unit (a1) having an organic group having one or more CH ₃ partial structures which is stable to an acid in a side chain portion.
The resin (P) has the repeating unit (a1) having an organic group that is stable against acid in the side chain portion together with the repeating unit represented by the general formula (1). When the hydrophobicity is improved and the exposure scanning speed is set to an ultra-high speed, the followability of the immersion liquid to the exposure apparatus can be further increased, and the immersion defects tend to be further reduced.

Here, the CH ₃ partial structure possessed by the side chain moiety in the repeating unit (a1) (hereinafter also simply referred to as “side chain CH ₃ partial structure”) has a CH ₃ partial structure possessed by an ethyl group, a propyl group or the like. It is included.
On the other hand, a methyl group directly bonded to the main chain of the repeating unit (a1) (for example, α-methyl group of the repeating unit having a methacrylic acid structure) is unevenly distributed on the surface of the resin (P) due to the influence of the main chain. Therefore, it is not included in the CH ₃ partial structure in the present invention.

More specifically, the resin (P) includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R ₁₁ to R ₁₄ are CH ₃ “as is”, the CH ₃ is not included in the CH ₃ partial structure of the side chain moiety in the present invention.
Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed that it has “one” CH ₃ partial structure in the present invention.

In the general formula (M), R ₁₁ to R ₁₄ each independently represents a side chain portion.
Examples of R ₁₁ to R _{14 in the} side chain portion include a hydrogen atom or a monovalent organic group.
Examples of the monovalent organic group for R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The repeating unit (a1) is not particularly limited as long as it has an acid group in the side chain portion and has one or more CH ₃ partial structures, but the following general formula (5) It is preferable that it is a repeating unit represented by these.

In the general formula (5), Za represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
Ra represents an alkyl group or a cycloalkyl group having one or more CH ₃ partial structures and stable to an acid. Here, the alkyl group or cycloalkyl group that is stable to an acid does not have an acid-decomposable group (a group that decomposes by the action of an acid to generate a polar group such as a carboxy group). , An alkyl group or a cycloalkyl group is preferable.

The alkyl group of Za is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is more preferable. .
As a halogen atom of Za, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A fluorine atom or a chlorine atom is preferable.

Za is preferably a hydrogen atom or a methyl group.
Ra includes an alkyl group or a cycloalkyl group having one or more CH ₃ partial structures. The above cycloalkyl group may further have an alkyl group as a substituent.
Ra is preferably an unsubstituted alkyl group or an unsubstituted cycloalkyl group substituted with an alkyl group.
The alkyl group or cycloalkyl group having one or more CH ₃ partial structures as Ra and stable to an acid preferably has 2 to 10 CH ₃ partial structures, preferably 2 to 8 It is more preferable to have no more.

The repeating unit (a1) is preferably an acid-stable (non-acid-decomposable) repeating unit. Specifically, the repeating unit (a1) is a repeating unit having no group that decomposes by the action of an acid to generate a polar group. Preferably there is.

When the resin (P) has a repeating unit (a1), the content of the repeating unit (a1) is preferably 10 to 90 mol%, preferably 10 to 80 mol%, based on all repeating units in the resin (P). More preferred is 15 to 60 mol%.

Preferred specific examples of the repeating unit (a1) are listed below. Note that the present invention is not limited to this. TMS represents a trimethylsilyl group.

It is preferable that the resin (P) has a repeating unit (a2) having a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer.
When the resin (P) has the repeating unit (a2) together with the repeating unit represented by the general formula (1), it is possible to further improve the affinity of the resist film to the alkaline developer during development, and development defects Tends to be further reduced.

The repeating unit (a2) is not particularly limited as long as it is a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer, but is represented by the following general formula (6) or (7). It is preferably a repeating unit.

Examples of the alkyl group for Zb include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, and pentyl group). A methyl group is preferred.

As a halogen atom of Zb, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A fluorine atom or a chlorine atom is preferable.
Zb is preferably a fluorine atom, a chlorine atom, a methyl group or a hydrogen atom, more preferably a fluorine atom or a methyl group.

The monovalent organic group as R ₆₁ and R ₆₂ is not particularly limited, and examples thereof include alkyl groups (preferably having 1 to 4 carbon atoms), cycloalkyl groups (preferably having 6 to 10 carbon atoms), and aryl groups. And a group (preferably having a carbon number of 6 to 10). The monovalent substituent as R ₁₁ and R ₁₂ may further have a substituent. Examples of such a further substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom. An atom, a hydroxyl group, an alkoxy group (preferably having 1 to 4 carbon atoms), a carboxy group, and the like can be given.

The electron withdrawing group as Rd is a partial structure represented by the following formula (EW). * In the formula (EW) represents a bond.

In formula (EW), n _ew is the number of repeating linking groups represented by —C (R _ew1 ) (R _ew2 ) —, and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond, indicating that Y _ew1 is directly bonded.
Y _ew1 represents a halogen atom, a cyano group, a nitro group, an aryl group substituted with a halo (cyclo) alkyl group, a haloaryl group, or a haloalkyl group represented by -C (R _f1 ) (R _f2 ) -R _f3 described later , An oxy group, a carbonyl group, a sulfonyl group, a sulfinyl group, and combinations thereof. _However, if _{Y ew1} is a halogen atom, a cyano group or a nitro _{group, n ew} is 1.
R _ew1 and R _ew2 each independently represent an arbitrary substituent, such as a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms) or an aryl group ( Preferably, it represents 6 to 10 carbon atoms.
At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.
The “halo (cyclo) alkyl group” represents an alkyl group and a cycloalkyl group that are at least partially halogenated, and the “haloaryl group” represents an aryl group that is at least partially halogenated.

Y _ew1 is preferably a halogen atom, a halo (cyclo) alkyl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , an haloaryl group, or an aryl group substituted with a haloalkyl group.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group. Represents a fluoromethyl group.
R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, which may be substituted with a halogen atom (preferably a fluorine atom), and more preferably R _f2 and R _f3 are (halo) alkyl groups. Or a (halo) cycloalkyl group. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.
_{Examples of} the ring formed by connecting R _f2 and R _f3 include a (halo) cycloalkyl ring.

The (halo) alkyl group in R _f1 to R _f3 may be linear or branched, and the linear (halo) alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, For example, methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decanyl group and the like, and groups in which these are halogenated can be mentioned. The branched (halo) alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, such as isopropyl group, isobutyl group, t-butyl group, isopentyl group, t-pentyl group, isohexyl group, Examples thereof include a t-hexyl group, an isoheptyl group, a t-heptyl group, an isooctyl group, a t-octyl group, an isononyl group, a t-decanoyl group, and a group in which these are halogenated. Preferred are those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group, and groups in which these are halogenated.

The (halo) cycloalkyl group in R _f1 to R _f3 or in the ring formed by linking R _f2 and R _f3 may be monocyclic or polycyclic. In the case of a polycyclic type, the (halo) cycloalkyl group may be a bridged type. That is, in this case, the (halo) cycloalkyl group may have a bridged structure.
As the monocyclic type, a (halo) cycloalkyl group having 3 to 8 carbon atoms is preferable. For example, (halo) cyclopropyl group, (halo) cyclopentyl group, (halo) cyclohexyl group, (halo) cyclobutyl group, (halo) ) A cyclooctyl group and the like can be mentioned.
Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and (halo) cycloalkyl groups having 6 to 20 carbon atoms are preferable, for example, (halo) adamantyl groups, (Halo) norbornyl group, (halo) isobornyl group, (halo) camphanyl group, (halo) dicyclopentyl group, (halo) α-pinel group, (halo) tricyclodecanyl group, (halo) tetocyclododecyl group, Mention may be made of (halo) androstanyl groups.
Examples of these (halo) cycloalkyl groups include those represented by the following formula and groups in which they are halogenated. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

Preferred examples of the alicyclic moiety include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group. And cyclododecanyl group. More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.
Examples of the substituent for these alicyclic moieties include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group. Preferred examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the substituent that the alkyl group and alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).

In R _f2 and _{R f3,} _or (halo) cycloalkyl group in the ring and _{R f2} and _{R f3} is formed by connecting is represented by more preferably _{_{-C (n) F (2n-}} 2) H A fluorocycloalkyl group is mentioned. Here, the number n of carbon atoms is not particularly limited, but preferably 5 to 13 and more preferably 6.

_Examples of the (per) haloaryl group in Y _ew1 or R _f1 include a perfluoroaryl group represented by —C _(n) F _(n−1) . Here, the number n of carbon atoms is not particularly limited, but preferably 5 to 13 and more preferably 6.

_Examples of the haloalkyl group in the aryl group substituted with the haloalkyl group in Y _{ew1 include} a haloalkyl group in a halo (cyclo) alkyl group represented by —C (R _f1 ) (R _f2 ) —R _f3 .
The aryl group in the aryl group substituted with the haloalkyl group in Y _ew1 is not particularly limited, and examples thereof include an aryl group having 6 to 10 carbon atoms (not including the carbon number of the haloalkyl group).

The ring that may be formed by connecting at least two of R _ew1 , R _ew2 and Y _ew1 to each other is preferably a cycloalkyl group or a heterocyclic group.

Each group and each ring constituting the partial structure represented by the above formula (EW) described above may further have a substituent. Examples of the further substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, Bromine, iodine), nitro group, cyano group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and other alkyl groups, methoxy group, ethoxy group, hydroxyethoxy Group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, benzyl group, phenethyl group, Aralkyl groups such as cumyl groups, aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, Nylyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, alkenyl group such as vinyl group, propenyl group, allyl, vinyloxy group, propenyloxy group, allyloxy group, butenyloxy group, phenyl group, An aryl group such as a naphthyl group, an aryloxy group such as a phenoxy group, an aryloxycarbonyl group such as a benzoyloxy group, and the like can be given. However, ionic groups are not included in the further substituents.

Rd is preferably an alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group, and more preferably an alkyl group substituted with a halogen atom (haloalkyl group). Preferably, it is a fluoroalkyl group. The alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
More specifically, Rd is an atomic group represented by —C (R ′ ₁ ) (R ′ _f1 ) (R ′ _f2 ) or —C (R ′ ₁ ) (R ′ ₂ ) (R ′ _f1 ) It is preferable that Here, R ′ ₁ and R ′ ₂ each independently represent a hydrogen atom or an alkyl group that is not substituted (preferably unsubstituted) with an electron-withdrawing group. R ′ _f1 and R ′ _f2 each independently represent a halogen atom, a cyano group, a nitro group, or a perfluoroalkyl group.
The alkyl group as R ′ ₁ and R ′ ₂ may be linear or branched, and preferably has 1 to 6 carbon atoms.
The perfluoroalkyl group as R ′ _f1 and R ′ _f2 may be linear or branched, and preferably has 1 to 6 carbon atoms.
Preferable specific examples of Rd include —CF ₃ , —C ₂ F ₅ , —C ₃ F ₇ , —C ₄ F ₉ , —CF (CF ₃ ) ₂ , —CF (CF ₃ ) C ₂ F ₅ , — CF ₂ CF (CF ₃ ) ₂ , —C (CF ₃ ) ₃ , —C ₅ F ₁₁ , —C ₆ F ₁₃ , —C ₇ F ₁₅ , —C ₈ F ₁₇ , —CH ₂ CF ₃ , —CH ₂ C ₂ F ₅ , —CH ₂ C ₃ F ₇ , —CH (CF ₃ ) ₂ , —CH (CF ₃ ) C ₂ F ₅ , —CH ₂ CF (CF ₃ ) ₂ , —CH ₂ CN, etc. Among them, —CF ₃ , —C ₂ F ₅ , —C ₃ F ₇ , —C ₄ F ₉ , —CH ₂ CF ₃ , —CH ₂ C ₂ F ₅ , —CH ₂ C ₃ F ₇ , —CH _{_{_{(CF 3) 2, -CH 2}}} CN are _{_{_{_{preferred, -CH 2 CF 3, -CH 2}}}} C 2 F 5, -CH 2 C 3 F _{_{, -CH (CF 3) 2,}} -CH 2 CN , more _{_{_{_{preferably, -CH 2 C 2 F 5,}}}} -CH (CF 3) 2, more preferably _{_{_{_{-CH 2 CN, -CH 2 C 2}}}} F 5, - CH (CF ₃ ) ₂ is particularly preferred.

Specific examples and preferred examples of the alkyl group of Zc are the same as those described for the alkyl group as Zb in the general formula (1).
Specific examples and preferred examples of the halogen atom for Zc are the same as those described for the halogen atom as Zb in the general formula (1).
Zc is preferably a fluorine atom, a chlorine atom, a methyl group or a hydrogen atom, more preferably a fluorine atom or a methyl group.

The alkylene group and cycloalkylene group of L ₁ may have a substituent.
The alkylene group in L ₁ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. A preferred cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. In order to exhibit the effects of the present invention, an alkylene group is more preferable, and a methylene group is particularly preferable.

The divalent linking group as Re is, for example, a single bond, an ether bond, an ester bond, an amide bond, a urethane bond (—O—C (═O) —NR— or —NR—C (═O) —O—). Or a urea bond (group represented by —NR—C (═O) —NR—). Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group each independently. Re is preferably a single bond or an ester bond.

N1 represents an integer of 0 to 5, preferably an integer of 0 to 1.

Examples of the alkylene group for Xa include alkylene groups having 1 to 2 carbon atoms, and a methylene group is preferred.
Xa is preferably an alkylene group.

Rf represents an electron withdrawing group.
The electron withdrawing group of Rf is preferably a group represented by the following general formula (A).

In the general formula (A), Y represents a group that is decomposed by the action of an alkali developer and increases the solubility in the alkali developer. E represents a monovalent group.

Y includes carboxylic acid ester group: —COO— or OCO—, acid anhydride group: —C (O) OC (O) —, acid imide group: —NHCONH—, carboxylic acid thioester group: —COS—, carbonic acid An ester group: —OC (O) O—, a sulfate ester group: —OSO ₂ O—, and a sulfonate ester group: —SO ₂ O— can be mentioned, and a carboxylic ester group is preferred.

E is not particularly limited as long as the group represented by the general formula (A) is a group that is electron withdrawing, but is preferably a partial structure represented by the above formula (EW).
It is preferable that E is an electron-attracting group because the group represented by the general formula (A) is decomposed by the action of an alkali developer, and the solubility in the alkali developer tends to further increase. .
E is preferably the same as that described in the partial structure represented by the above formula (EW) as the electron-withdrawing group of Rd.

When the resin (P) has a repeating unit (a2), the content of the repeating unit (a2) is preferably 10 to 90 mol%, more preferably 15 to 80 mol%, based on all repeating units in the resin (P). More preferred is 20 to 80 mol%.

Preferred specific examples of the repeating unit (a2) are listed below. Note that the present invention is not limited to this.

The resin (P) can further have a repeating unit (a3) as long as the effects of the present invention are not impaired. Although it does not specifically limit as a further repeating unit (a3), For example, the repeating unit which has a polar group can be mentioned.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a fluorinated alcohol group.
Preferred specific examples of the further repeating unit (a3) are listed below. Note that the present invention is not limited to this.

When the exposure scanning speed is set to an ultra-high speed, the followability of the immersion liquid to the exposure apparatus is further increased and the solubility in the developer is increased. Therefore, the resin (P) contains the repeating unit ( It is more preferable to have a1) and the repeating unit (a2).

Further, the repeating unit represented by the general formula (1) may or may not be a repeating unit having a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer.
In other words, the repeating unit represented by the general formula (1) may be the same as or different from the repeating unit represented by the general formula (a2).

As a preferable embodiment in which the repeating unit represented by the general formula (1) is a repeating unit having a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer, the general formula ( An embodiment in which the repeating unit represented by 3) or (4) corresponds to a repeating unit having a group that increases the solubility in an alkali developer is mentioned.

The weight average molecular weight (Mw) of the resin (P) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and most preferably 5,000 as a polystyrene conversion value by GPC method. ~ 15,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased so that film forming property is deteriorated. Can be prevented.
Another particularly preferable form of the weight average molecular weight of the resin (P) is 3,000 to 9,500 in terms of polystyrene by GPC method. The dispersity (molecular weight distribution) (hereinafter also referred to as Mw / Mn or Pd) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to Those in the range of 2.0 are used. The smaller the degree of dispersion, the better the resolution and the resist shape, the smoother the side wall of the resist pattern, and the better the roughness.

The resin (P) is naturally low in impurities such as metals, and the residual monomer and oligomer components are preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and 0 to 1%. Mass% is even more preferred. Thereby, a resist having no change over time such as foreign matter in liquid or sensitivity can be obtained.

Specific examples of the resin (P) are shown in the table below, but the present invention is not limited to these. In the table below, the composition ratio of the repeating units indicates a molar ratio. Moreover, the repeating unit in the composition described in the following table will be described later (Ph represents a phenyl group, and TMS represents a trimethylsilyl group).

Resin (P) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.

Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like An amide solvent; a solvent capable of dissolving a resist composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone described later; More preferably, polymerization is performed using the same solvent as the solvent used in the resist composition. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction product is 5 to 50% by mass, preferably 10 to 45% by mass.

The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 40 ° C. to 100 ° C.
Purification can be accomplished by using a liquid-liquid extraction method that removes residual monomers and oligomer components by washing with water or an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. In a solid state such as reprecipitation method by removing the residual monomer by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, or washing the filtered resin slurry with the poor solvent Ordinary methods such as the purification method can be applied.

The content of the resin (P) in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.01 to 10% by mass based on the total solid content of the actinic ray- or radiation-sensitive resin composition, More preferably, it is 0.1 to 10% by mass, still more preferably 0.1 to 9% by mass, and particularly preferably 0.5 to 8% by mass.
In addition, resin (P) may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of resin (P) together, it is preferable that total content is in the said range.

When an actinic ray-sensitive or radiation-sensitive film is formed, the dynamic receding contact angle of water on the actinic ray-sensitive or radiation-sensitive film (temperature: 23 ° C., relative humidity: 45%) is determined by scanning exposure. Assuming that the speed is an ultra-high speed (for example, 700 mm / second or more), it is preferably 80 ° or more, and more preferably 85 ° or more. The water dynamic receding contact angle is typically 90 ° or less.
Such a dynamic receding contact angle of water can be suitably achieved, for example, by setting the content of the resin (P) within the above range.

<Hydrophobic resin (P ')>
The composition of the present invention may contain a hydrophobic resin (P ′) different from the resin (P). If the hydrophobic resin (P ′) does not have the repeating unit represented by the general formula (1), the hydrophobic resin (P ′) may have the above-described repeating unit that the resin (P) may have. The preferred range of the content of these repeating units based on all repeating units of the hydrophobic resin (P ′) is the same as the above-described range in the resin (P).
Moreover, the preferable range of the weight average molecular weight of the resin (P ′), the dispersity, and the content based on the total solid content of the composition of the present invention is the same as the above-described range in the resin (P).

<Resin (A)>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin having a group (hereinafter also referred to as “acid-decomposable group”) that is decomposed by the action of an acid and increases in polarity (hereinafter referred to as “acid-decomposable group” Or “resin (A)”.
In this case, in the pattern forming method of the present invention, typically, when an alkaline developer is employed as the developer, a positive pattern is suitably formed, and when an organic developer is employed as the developer. The negative pattern is preferably formed.

As the resin (A), known resins can be used as appropriate. For example, paragraphs <0055> to <0191> in US Patent Application Publication No. 2016 / 0274458A1, paragraphs <0035> to <0085> in US Patent Application Publication No. 2015 / 0004544A1, and US Patent Application Publication No. 2016 / 0147150A1. Known resins disclosed in paragraphs <0045> to <0090> of the specification can be suitably used as the resin (A).

The acid-decomposable group preferably has a structure in which a polar group is protected with a group capable of decomposing and leaving by the action of an acid (leaving group).
As polar groups, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Acid groups (groups dissociating in an aqueous 2.38 mass% tetramethylammonium hydroxide solution), alcoholic hydroxyl groups, and the like.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). Excludes aliphatic alcohols substituted with sexual groups (for example, hexafluoroisopropanol groups). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

Preferred polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.

A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving by the action of an acid (leaving group).
Examples of the group (leaving group) leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and — And C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ).
In the formula, R ₃₆ to R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl Group, and octyl group.
The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group. Group, and androstanyl group, etc. can be mentioned. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The ring formed by combining R ₃₆ and R ₃₇ with each other is preferably a cycloalkyl group (monocyclic or polycyclic). As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. .

As the acid-decomposable group, a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group is preferable, and an acetal ester group or a tertiary alkyl ester group is more preferable.

The resin (A) preferably has a repeating unit represented by the following general formula (AI) as a repeating unit having an acid-decomposable group.

In the general formula (AI), Xa ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group.
T represents a single bond or a divalent linking group.
Rx ₁ to Rx ₃ each independently represents an alkyl group or a cycloalkyl group.
Any two of Rx ₁ to Rx ₃ may be bonded to form a ring structure, or may not be formed.

Examples of the divalent linking group for T include an alkylene group, an arylene group, —COO—Rt—, —O—Rt—, and the like. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an arylene group.
T is preferably a single bond or —COO—Rt—. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably —CH ₂ —, — (CH ₂ ) ₂ —, or — (CH ₂ ) ₃ —. More preferably, T is a single bond.

Xa ₁ is preferably a hydrogen atom or an alkyl group.
The alkyl group of Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
The alkyl group of Xa ₁ preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group. The alkyl group of Xa ₁ is preferably a methyl group.

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. Group, t-butyl group and the like are preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. In the alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ , a part of the carbon-carbon bond may be a double bond.
Examples of the cycloalkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, and the like. The polycyclic cycloalkyl group is preferable.

The ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ includes a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, a norbornane ring, a tetracyclo ring, or the like. A polycyclic cycloalkyl ring such as a decane ring, a tetracyclododecane ring and an adamantane ring is preferred. A cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable. As the ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ , the structures shown below are also preferable.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (AI) are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to the case where Xa ₁ in formula (AI) is a methyl group, and Xa ₁ can be optionally substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

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

Resin (A) is decomposed by the action of an acid described in paragraphs <0363> to <0364> of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having an acid-decomposable group. You may have a repeating unit containing the group which produces | generates a hydroxyl group.

Resin (A) may contain one type of repeating unit having an acid-decomposable group, or two or more types in combination.

The content of the repeating unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of repeating units having an acid-decomposable group, the total) is based on the total repeating units of the resin (A), 10 to 90 mol% is preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is still more preferable.

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.

Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable. Other ring structures in which other ring structures are condensed to form a bicyclo structure or spiro structure in a membered lactone structure, or other bicyclic structures in which a bicyclo structure or a spiro structure is formed in a 5- to 7-membered ring sultone structure More preferably, the ring is condensed. It has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3) More preferably, it has a repeating unit. A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), (LC1-16), (LC1-21) and (SL1-1).

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

The repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (III).

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

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

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

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

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

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

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

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

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

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

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

Other specific examples of the repeating unit having a polar group include repeating units disclosed in paragraphs <0415> to <0433> of US Patent Application Publication No. 2016 / 0070167A1.
Resin (A) may contain the repeating unit which has a polar group individually by 1 type, and may contain 2 or more types together.
The content of the repeating unit having a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (A).

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

In addition, specific examples of the repeating unit having neither an acid-decomposable group nor a polar group include the repeating unit disclosed in paragraph <0433> of US Patent Application Publication No. 2016 / 0070167A1. Can do.
Resin (A) may contain the repeating unit which has neither an acid-decomposable group nor a polar group individually by 1 type, and may contain 2 or more types together.
The content of the repeating unit having neither an acid-decomposable group nor a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, based on all repeating units in the resin (A). 5 to 25 mol% is more preferable.

Resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general required characteristics of resist, in addition to the above repeating structural units. For this purpose, various repeating structural units can be included. Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a monomer.

Examples of the monomer include compounds having one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Can be mentioned.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.
In the resin (A), the content molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.

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

In the resin (A), it is preferable that all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, it is preferable that the acrylate-based repeating unit is 50 mol% or less with respect to all 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 contains a repeating unit having an aromatic hydrocarbon group. It is more preferable that the resin (A) contains 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 structure protected with.
The content of the repeating unit having an aromatic hydrocarbon group contained in the resin (A) is preferably from 30 to 100 mol%, more preferably from 40 to 100 mol%, based on all repeating units in the resin (A). 50 to 100 mol% is more preferable.

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

Resin (A) may be used individually by 1 type, and may use 2 or more types together.
The content of the resin (A) in the total solid content of the composition of the present invention is generally 20% by mass or more. 40 mass% or more is preferable, 60 mass% or more is more preferable, and 70 mass% or more is still more preferable. Although an upper limit in particular is not restrict | limited, 99.5 mass% or less is preferable, 99 mass% or less is more preferable, and 97 mass% or less is still more preferable.

<Photoacid generator (C)>
The composition of the present invention typically contains a photoacid generator (hereinafter also referred to as “photoacid generator (C)”).
The photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation.
As a photo-acid generator, the compound which generate | occur | produces an organic acid by irradiation of actinic light or a radiation is preferable. Examples 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, known compounds that generate an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof. For example, Paragraphs <0125> to <0319> of US Patent Application Publication No. 2016 / 0070167A1, Paragraphs <0086> to <0094> of US Patent Application Publication No. 2015 / 0004544A1, and US Patent Application Publication No. 2016 / 0237190A1. Known compounds disclosed in paragraphs <0323> to <0402> of the specification can be suitably used as the photoacid generator (C).

As a suitable aspect of a photo-acid generator (C), the compound represented by the following general formula (ZI), (ZII), and (ZIII) is mentioned, for example.

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two _{members out} of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group) and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —. it can.
Z ⁻ represents an anion.

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

First, the compound (ZI-1) will be described.
Compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, a part of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group optionally contained in the arylsulfonium compound is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. A group is preferred, 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 each independently an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having a carbon number) 6 to 14), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted.

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

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

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

In general formula (ZI-3), R _1c to R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cyclo Represents an alkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group;
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. The ring structure may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring structure include a 3- to 10-membered ring, a 4- to 8-membered ring is preferable, and a 5- or 6-membered ring is more preferable.

_{Examples of} the group formed by combining any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by combining R _5c and R _6c , and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
Zc ^- represents an anion.

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

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

In general formula (ZI-4), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched and preferably have 1 to 10 carbon atoms, and may be a methyl group, an ethyl group, n- A butyl group or a t-butyl group is more preferable.

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

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, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 3 carbon atoms). 15), aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.
Z ⁻ represents an anion.

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

In general formula (3), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
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, and when there are a plurality of R ₄ and R ₅ , R ₄ and R ₅ are the same But it can be different.
L represents a divalent linking group, and when there are a plurality of L, Ls may be the same or different.
W represents an organic group containing a cyclic structure.
o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is more preferably a fluorine atom or CF ₃ . In particular, it is preferable that both Xf are fluorine atoms.

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

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

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

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

The cyclic organic group may have a substituent. Examples of this substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic or spirocyclic). Well, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonic acid An ester group is mentioned. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

Formula (3) As the anion represented _{^{_{_{by, SO 3 - -CF 2 -CH 2}}}} -OCO- (L) q'-W, SO 3 - -CF 2 -CHF-CH 2 -OCO- (L) _{^{_{q'-W, SO 3 - -CF}}} 2 -COO- (L) q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q-W, SO 3 - -CF _2- CH (CF ₃ ) —OCO— (L) q′—W is preferred. Here, L, q, and W are the same as those in the general formula (3). q ′ represents an integer of 0 to 10.

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

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

Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in the general formula (ZI-4) ^- as the following general formula (5) The anion represented is preferred.

In the general formula (5), each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Xb each independently represents an organic group having no hydrogen atom or fluorine atom. The definitions and preferred embodiments of o, p, q, R ₄ , R ₅ , L, and W are the same as those in the general formula (3).

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

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

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

N represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and most preferably 3.

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 sulfone group, a sulfonate ester group, an ester group, and a group composed of a combination of two or more thereof. .

B represents a hydrocarbon group.

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

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

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

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

The acid generator may be in the form of a low molecular compound or may be in a form incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
The photoacid generator is preferably in the form of a low molecular compound.
When the acid generator is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
When the acid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above or in a resin different from the resin (A).
An acid generator may be used individually by 1 type, and may use 2 or more types together.

The content of the acid generator in the composition (when there are a plurality of types) is preferably 0.1 to 35% by mass, and preferably 0.5 to 25% by mass based on the total solid content of the composition. More preferred is 3 to 20% by mass, still more preferred is 3 to 15% by mass.
When the compound represented by the above general formula (ZI-3) or (ZI-4) is contained as the acid generator, the content of the acid generator contained in the composition (when there are plural kinds, the total thereof) 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 controller (D). The acid diffusion controller (D) acts as a quencher that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. . For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, an onium salt (DC) that becomes a weak acid relative to an acid generator, a nitrogen atom And a low molecular compound (DD) having a group capable of leaving by the action of an acid, an onium salt compound (DE) having a nitrogen atom in the cation moiety, or the like can be used as an acid diffusion controller. In the composition of the present invention, a known acid diffusion controller can be used as appropriate. For example, paragraphs <0627> to <0664> of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs <0095> to <0187> of Publication No. 2015 / 0004544A1, and U.S. Patent Application Publication No. 2016 / 0237190A1. 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 preferably used as the acid diffusion control agent (D). it can.

The basic compound (DA) is preferably a compound having a structure represented by the following formulas (A) to (E).

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

The alkyl group in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
Regarding the alkyl group, the alkyl group having a substituent is preferably 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.
The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

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

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

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

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

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

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

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

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

In the composition of the present invention, an onium salt (DC) that is a weak acid relative to the acid generator can be used as an acid diffusion controller.
When an acid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the acid generator are mixed and used, it is generated from the acid generator by irradiation with actinic rays or radiation. When the acid collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to yield an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

The onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

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

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

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

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

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. An alkyl group, a cycloalkyl group, or an aryl group is preferable.

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

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

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

Rb is preferably a linear or branched alkyl group, a cycloalkyl group, or an aryl group, and more preferably a linear or branched alkyl group or a cycloalkyl group.
Examples of the ring formed by connecting two Rb to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
Specific examples of the group represented by the general formula (d-1) include, but are not limited to, the structures 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, two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are each independently substituted with the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb. A good group may be substituted with the same group as described above.

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

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

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

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

<Solvent (F)>
The composition of the present invention usually contains 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, and Patent Publication No. 2016 / 0237190A1. Known solvents disclosed in paragraphs <0424> to <0426> of the specification and paragraphs <0357> to <0366> of U.S. 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, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), Examples thereof include an organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

As an organic solvent, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate, but the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether or alkyl lactate, and propylene glycol monomethyl ether. (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferable. As the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, a monoketone compound which may contain a ring, cyclic lactone, alkyl acetate, etc. are preferable. 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, More preferred is cyclopentanone or 2-heptanone. As the solvent not containing a hydroxyl group, propylene carbonate is also preferable.

The mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. preferable. A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is preferable from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, may be a propylene glycol monomethyl ether acetate single solvent, or may be two or more mixed solvents containing propylene glycol monomethyl ether acetate.

<Surfactant (H)>
The composition of the present invention may or may not contain a surfactant. In the case of containing a surfactant, a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) ) Is preferred.

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, it is possible to obtain a resist pattern with good sensitivity and resolution and less adhesion and development defects. it can.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425.
In addition, surfactants other than 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, and 0.0005 to 1% by mass with respect to the total solid content of the composition. More preferred.
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 surface uneven distribution of the hydrophobic resin is increased. Thereby, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and water followability at the time of immersion exposure is improved.

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

<Preparation method>
The film thickness of the actinic ray-sensitive film or radiation-sensitive film made of the composition of the present invention is preferably 90 nm or less, and more preferably 85 nm or less, from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property or film forming property.
The solid content concentration of the composition of the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass. The solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.

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

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

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

The pattern forming method of the present invention includes (i) a step of forming an actinic ray-sensitive or radiation-sensitive film on a support with the above-described actinic ray-sensitive or radiation-sensitive resin composition (film formation step), (ii) ) A step of exposing the actinic ray-sensitive or radiation-sensitive film to an actinic ray or radiation (exposure step); and (iii) an actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation. A step of developing using the developer (developing step).

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

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

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

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

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

(Iii) In the developing step, an alkali developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer) may be used, but an alkali developer is preferably used.

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

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

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

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

As the alcohol solvent, amide solvent, ether solvent, and 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, still more preferably less than 10% by mass, and particularly preferably substantially free of moisture.
The content of the organic solvent in the organic developer is preferably 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and more preferably 90% by mass to 100% by mass with respect to the total amount of the developer. The following is more preferable, and 95% by mass or more and 100% by mass or less is particularly preferable.

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

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

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

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

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

(Iii) It is preferable to include a step of washing with a rinsing liquid (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 process or the rinsing process, a process for removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid may be added. Further, after the rinse treatment or the treatment with the supercritical fluid, a heat treatment may be performed in order to remove moisture remaining in the pattern.

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 resist pattern, and a solution containing a general organic solvent can be used. As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. It is preferable.
Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent are the same as those described in the developer containing an organic solvent.
As the rinse liquid used in the rinse process in this case, a rinse liquid containing a monohydric alcohol is more preferable.

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

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

The rinse solution may contain an appropriate amount of a surfactant.
In the rinsing step, the substrate that has been developed using the organic developer is washed with a rinse containing an organic solvent. The method of the cleaning process is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), or the like can be applied. In particular, it is preferable to perform a cleaning process by a spin coating method, rotate the substrate at a rotational speed of 2,000 to 4,000 rpm after the cleaning, and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. By this heating process, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is usually 40 to 160 ° C., preferably 70 to 95 ° C., and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

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

Examples of a method for removing impurities such as metals from the various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step. The filter is preferably a filter with reduced 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 with an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500).
Moreover, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. Alternatively, a method of performing distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) or the like can be mentioned. A filter that is applied to the raw materials that make up various preferred materials in order to reduce the metal to the ppt order by applying glass lining treatment to all the steps of the manufacturing equipment that synthesizes various resist component materials (binder, PAG, etc.) Preferable conditions for filtration are the same as those described above.

The various materials described above are disclosed in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351), Japanese Patent Application, It is preferably stored in a container described in Japanese Patent Application Publication No. 2017-13804 (Japanese Patent Laid-Open No. 2017-13804).

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 a resist pattern by plasma of hydrogen-containing gas disclosed in US Patent Application Publication No. 2015/0104957 can be cited. In addition, Japanese Patent Application Publication No. 2004-235468 (JP 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity
Known methods such as those described in “Enhancement” may be applied.
The resist pattern formed by the above-described method is, for example, a spacer disclosed in Japanese Patent Application Publication No. 1991-270227 (JP-A-3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as a process core.

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

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. The scope of the present invention is not limitedly interpreted by the following examples.

<Synthesis Example 1: Synthesis of Compound M1-1>
10.5 g of potassium fluoride was suspended in 100 g of acetone, and 30.0 g of (1) was further added. After stirring at room temperature for 1 hour, the reaction solution was cooled to −40 ° C. 16.4g (3) was added there, and it stirred at 0 degreeC for 2 hours. The reaction solution was added to 200.0 g of ice water to stop the reaction, and then the lower layer was taken out. Further, the lower layer was washed with 100 g of water three times to obtain 20.21 g of the compound (M1-1).

<Synthesis Example 3: Synthesis of Resin P-77>
Under a nitrogen stream, 13.7 g of cyclohexanone was placed in a three-necked flask and heated to 70 ° C. A solution prepared by dissolving 21.6 g of (M1-1), 2.98 g of (4) and 1.24 g of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) in 30.8 g of cyclohexanone was added for 4 hours. It was dripped over. After completion of dropping, the reaction was further continued at 70 ° C. for 2 hours. The reaction mixture was allowed to cool and then added dropwise over 20 minutes to a mixture of 900 ml of methanol / 100 ml of water. The precipitated powder was collected by filtration and dried, yielding 19 g of Resin (P-77). The weight average molecular weight of the obtained resin was 7000 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.6.

Resins (P-1) to (P-160) listed above were synthesized in the same manner as resin (P-77).

Thereafter, resins (S-1) to (S-4) were synthesized in the same manner.

The structures, composition ratios (molar ratios), weight average molecular weights, and dispersities of the resins (P-1) to (P-160) are as described above.

The structures, composition ratios (molar ratios), weight average molecular weights, and dispersities of the resins (S-1) to (S-4) are as follows.

<Synthesis Example 4: Synthesis of Resin (1)>
Under a nitrogen stream, 8.6 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. To this was added 9.8 g of 2-adamantyl isopropyl methacrylate, 4.4 g of dihydroxyadamantyl methacrylate, 8.9 g of norbornane lactone methacrylate, polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), and 8 mol% of cyclohexanone 79 g with respect to the monomer. The solution dissolved in was added dropwise over 6 hours. After completion of dropping, the reaction was further continued at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise over 20 minutes to a mixture of 800 m of hexane / 200 ml of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain 19 g of Resin (1). The weight average molecular weight of the obtained resin was 8800 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.9.
Similarly, another resin (A) shown below was synthesized.

The structure of the acid-decomposable resin (A) used in the examples is shown below. Table 2 below shows the molar ratio of repeating units in each resin (in order from the left in the structural formula), weight average molecular weight (Mw), and dispersity (Mw / Mn).

[Examples 1-A to 36-A, Comparative Examples 1-A ′ to 4-A ′ (ArF immersion exposure)]
(1) Coating solution preparation and coating of resist composition An organic antireflection film ARC29SR (manufactured by Brewer) is applied on a silicon wafer and baked at 205 ° C for 60 seconds to form an antireflection film having a thickness of 98 nm. A resist composition shown in the following table was applied thereon and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 90 nm. Here, the resist composition is prepared by preparing a solution having a solid content concentration of 4% by mass and filtering the solution through a polyethylene filter having a pore size of 0.05 μm. Moreover, resin (P) and resin (P ') were used by content (displayed with the mass% on the basis of the total solid of a composition) of Table 3 below.

(2) ArF exposure and development 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) with a line width of 75 nm Exposure was through a 6% halftone mask with a 1: 1 line and space pattern. Ultra pure water was used as the immersion liquid. Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.

(3) Evaluation of resist pattern Using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.), the obtained resist pattern was subjected to immersion defects, development defects, dynamic receding contact angles ( DRCA: Dynamic Recating Contact Angle) was evaluated. The results are shown in the table below.

(Immersion defect)
The development residue (scum) in a resist pattern with a line width of 75 nm was observed using a scanning electron microscope (S-9220 manufactured by Hitachi). A was a residue that did not occur at all, A was a residue that was severely generated, The middle was B and C (B has less residue than C). At that time, the exposure scan speed was 700 mm / s.

[Development defects]
A defect inspection apparatus KLA2360 (trade name) manufactured by KLA Tencor Co., Ltd. for a pattern (exposure scan speed is 700 mm / s) formed on a silicon wafer (12-inch diameter) as described above. ), The pixel size of the defect inspection device is set to 0.16 μm, the threshold value is set to 20, and measurement is performed in a random mode to detect a development defect extracted from a difference caused by superimposition of the comparison image and the pixel unit. The number of development defects per unit area (pieces / cm 2) was calculated. One inch is 0.0254 m. A value of less than 0.5 was designated as A, 0.5 or more and less than 0.7 as B, 0.7 or more and less than 1.0 as C, and 1.0 or more as D. A smaller value indicates better performance.

[Dynamic receding contact angle (DRCA)]
The prepared resist composition was applied on a silicon wafer (8-inch diameter), and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. The receding contact angle of water droplets was measured by the expansion / contraction method of a dynamic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). An initial droplet size of 35 μL was sucked at a speed of 6 μL / sec for 5 seconds, and a value with a stable dynamic contact angle during suction was defined as a receding contact angle. The measurement environment is 23 ° C. and relative humidity 45%. The larger the receding contact angle value, the higher the water followability with respect to the ultra high scanning speed.

The photoacid generator, acid diffusion controller, resin (P ′), surfactant, and solvent in Table 3 are as follows.

[Photoacid generator]

[Acid diffusion control agent]

Note that Bu represents a butyl group.

[Resin (P ')]
The molar ratio of the repeating unit in each resin, the weight average molecular weight (Mw), and the dispersity (Mw / Mn) are shown.

[Surfactant]
W-1: Megafac F176 (Dainippon Ink Chemical Co., Ltd., fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd., fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., silicon-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: PF656 (manufactured by OMNOVA, fluorine-based)
W-6: PF6320 (manufactured by OMNOVA, fluorine-based)

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

From Table 3, the example using the composition containing the resin (P) has an ultra-high scanning speed (700 mm / s) compared to the comparative example using the composition not containing the resin (P). ), It was possible to reduce both immersion defects and development defects while having high followability of the immersion liquid to the exposure apparatus.

Claims

Actinic ray-sensitive or radiation-sensitive resin containing a resin (P) having a repeating unit represented by the following general formula (1), and a resin (A) having a group that is decomposed by the action of an acid to increase polarity Composition.

In the general formula (1),
Z represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R 11 OCH 2 —, or a group represented by R 12 OC (═O) CH 2 —. R 11 and R 12 each independently represents a monovalent substituent.
X represents an oxygen atom or a sulfur atom.
L represents a single bond or a (m + 1) -valent linking group.
R represents a group represented by the following formula (1-1).
m represents a positive integer. When m is 2 or more, the plurality of R may be the same as or different from each other. When L represents a single bond, m represents 1.

In the above formula (1-1),
* Represents a bond with L or X.
R 1 and R 1 ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (2).

In the general formula (2),
Z 2 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R 21 OCH 2 —, or a group represented by R 22 OC (═O) CH 2 —. R 21 and R 22 each independently represents a monovalent substituent.
X 2 represents an oxygen atom or a sulfur atom.
R 2 represents a group represented by the following formula (1-1).

In the above formula (1-1),
* Represents a bond to X 2.
R 1 and R 1 ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (3) or (4). .

In the general formula (3),
Z 3 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a group represented by R 31 OCH 2 —, or a group represented by R 32 OC (═O) CH 2 —. R 31 and R 32 each independently represents a monovalent substituent.
X 3 represents an oxygen atom or a sulfur atom.
L 3 represents a divalent linking group.
R 3 represents a group represented by the following formula (1-1).
In the general formula (4),
Z 4 represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.
X 4 represents an oxygen atom or a sulfur atom.
L 4 represents a divalent linking group.
R 4 represents a group represented by the following formula (1-1).

In the above formula (1-1),
* Represents a bond with —C (═O) — or —O—.
R 1 and R 1 ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
The resin (P) further has a repeating unit (a1) having an organic group having one or more CH 3 partial structures which is stable to an acid in a side chain portion. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to item 1.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein the repeating unit (a1) is a repeating unit represented by the following general formula (5).

In the general formula (5),
Za represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
Ra represents an alkyl group or a cycloalkyl group having one or more CH 3 partial structures and stable to an acid.
The resin (P) according to any one of claims 1 to 5, further comprising a repeating unit (a2) having a group that decomposes under the action of an alkali developer and increases the solubility in the alkali developer. An actinic ray-sensitive or radiation-sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 6, wherein the repeating unit (a2) is a repeating unit represented by the following general formula (6) or (7).

In the general formula (6),
Zb represents a hydrogen atom, an alkyl group, a halogen atom, a group represented by R 61 OCH 2 —, or a group represented by R 62 OC (═O) CH 2 —. R 61 and R 62 each independently represent a monovalent substituent.
Rd represents an electron withdrawing group.
In the general formula (7),
Zc represents a hydrogen atom, a halogen atom, or an alkyl group. L 1 represents an alkylene group, a cycloalkylene group, or a group formed by combining these. If L 1 is present in plurality, a plurality of L 1 may be be the same or different from each other.
Re represents a divalent linking group. When a plurality of Re are present, the plurality of Re may be the same as or different from each other.
n1 represents an integer of 0 to 5.
Xa represents an alkylene group, an oxygen atom, or a sulfur atom.
Rf represents an electron withdrawing group.
m1 represents an integer of 1 to 3.
An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7.
(I) forming an actinic ray-sensitive or radiation-sensitive film with the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7;
(Ii) irradiating the actinic ray-sensitive or radiation-sensitive film with an actinic ray or radiation; and
(Iii) A pattern forming method including a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation with a developer.
The pattern forming method according to claim 9, wherein the developer is an alkali developer.
The manufacturing method of an electronic device containing the pattern formation method of Claim 9 or 10.