WO2021172111A1

WO2021172111A1 - Pattern formation method, method for producing electronic device, and actinic ray-sensitive or radiation-sensitive resin composition

Info

Publication number: WO2021172111A1
Application number: PCT/JP2021/005775
Authority: WO
Inventors: 文博吉野; 佑真楜澤
Original assignee: 富士フイルム株式会社
Priority date: 2020-02-27
Filing date: 2021-02-16
Publication date: 2021-09-02
Also published as: JP7336018B2; TW202132374A; JPWO2021172111A1; CN114945868A

Abstract

The present invention provides a pattern formation method having (i) a step for forming an actinic ray-sensitive or radiation-sensitive film 700 nm or more thick by a specific actinic ray-sensitive or radiation-sensitive resin composition, (ii) a step for irradiating the actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation of a wavelength of 200 nm or less, and (iii) a step for developing the actinic ray-sensitive or radiation-sensitive film that has been irradiated with actinic rays or radiation of a wavelength of 200 nm or less by a developer; a method for producing an electronic device; and an actinic ray-sensitive or radiation-sensitive resin composition.

Description

Pattern forming method, manufacturing method of electronic device, and sensitive light-sensitive or radiation-sensitive resin composition

The present invention relates to a pattern forming method, a method for manufacturing an electronic device, a sensitive light-sensitive or radiation-sensitive resin composition.

Since the resist for KrF excimer laser (248 nm), a pattern forming method using chemical amplification has been used to compensate for the decrease in sensitivity due to light absorption. For example, in the positive chemical amplification method, first, the photoacid generator contained in the 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 the alkali-soluble group by the catalytic action of the generated acid. After that, development is performed using, for example, an alkaline solution. As a result, the exposed portion is removed to obtain a desired pattern.
In the above method, various alkaline 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.

Due to the miniaturization of semiconductor devices, the wavelength of the exposure light source has been shortened and the numerical aperture (NA) of the projection lens has been increased. 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 enhancing the resolving power, a method (that is, an immersion method) of filling a liquid having a high refractive index (hereinafter, also referred to as "immersion liquid") between the projection lens and the sample has been proposed.
Patent Document 1 describes (a) a resin whose polarity is increased by the action of an acid and whose solubility in a developing solution containing an organic solvent is reduced, and (B) an acid is generated by irradiation with active light or radiation. A step of forming a film having a film thickness of 200 nm or more by a chemically amplified resist composition containing a compound and (C) a solvent, (a) a step of exposing the film, and (c) the exposed film. , A method of forming a negative pattern including a step of developing with a developer containing an organic solvent.
Patent Document 2 describes a positive resist composition for an ion implantation process containing (A) a resin whose dissolution rate in an alkaline developer is increased by the action of an acid, and (B) a compound that generates an acid by irradiation with active light. Described is a positive resist composition for an ion implantation process, which comprises a resist film formed from the positive resist composition having a permeability of 30 to 60% with respect to 193 nm.

Japanese Patent Application Laid-Open No. 2012-133329 Japanese Patent Application Laid-Open No. 2006-189713

On the other hand, in recent years, there has been a demand for higher functionality of various electronic devices, and along with this, there is a demand for further improvement in the characteristics of resist patterns used for microfabrication.
Therefore, the present inventors examined the improvement of the resist performance in the resist pattern of a thick film (having a thickness of 700 nm or more), and found that the resist pattern had excellent resolution and cracks and resist patterns in the resist pattern. It was found that it is very difficult to suppress the peeling of the material at the same time.
An object of the present invention is that when a pattern is formed from a thick film (having a thickness of 700 nm or more), an actinic light-sensitive radiation-sensitive film, the resolution is excellent, and cracks in the resist pattern and peeling of the resist pattern are prevented. It is an object of the present invention to provide a pattern forming method using a suppressable actinic or radiation-sensitive resin composition, a method for producing an electronic device, and an actinic or radiation-sensitive resin composition.

That is, the present inventors have found that the above problem can be solved by the following configuration.

[1]
(I) A step of forming an actinic cheilitis or radiation-sensitive film having a film thickness of 700 nm or more with an actinic cheilitis or radiation-sensitive resin composition.
(Ii) A step of irradiating the above-mentioned sensitive light-sensitive or radiation-sensitive film with active light or radiation having a wavelength of 200 nm or less, and
(Iii) A step of developing a sensitive light-sensitive or radiation-sensitive film irradiated with active light or radiation having a wavelength of 200 nm or less using a developing solution.
It is a pattern forming method having
The actinic light-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-degradable group and (B) a photoacid generator.
A pattern forming method, wherein the polymer (A) has a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8000 or less.

[2]
The pattern forming method according to [1], wherein the (B) photoacid generator contains a compound represented by the following general formula (ZI-3) or a compound represented by the following general formula (ZI-4).

In the above general formula (ZI-3),
R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkenyl group.
R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or an aryl group. R ₂ and R ₃ may be connected to each other to form a ring.
R ₁ and R ₂ may be connected to each other to form a ring.
_RX and _Ry independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group. .. _RX and R _y may be linked to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, and an amide bond.
Z ^- represents an anion.

In the general formula (ZI-4),
l represents an integer of 0 to 2.
r represents an integer from 0 to 8.
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group.
R ₁₄ represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a cycloalkylsulfonyl group. R ₁₄ is, if there are two or more, plural R ₁₄ may being the same or different.
Each of R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Bonded to two R ₁₅ each other may form a ring. When two R ₁₅ are combined to form a ring together, the ring structure is an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
X ^- represents an anion.

[3]
The Z ^- or the wherein X ^-, a pattern forming method according to an anion represented by any one of the following formulas (A1) ~ (A3) [ 2].

In the above general formula (A1),
R ₂₁ and R ₂₂ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom. However, _{at least one of R 21} and R ₂₂ is a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom.
L represents a single bond or a divalent linking group.
X represents an organic group.
In the above general formula (A2),
R ₂₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, -C (= O) -Rx, or -S (= O) _2- Rx. Rx represents an organic group.
R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a fluorine atom.
A ₁ represents -C (= O)-or -S (= O) _2- .
R ₂₃ and R ₂₄ may be coupled to each other to form a ring.
In the above general formula (A3),
R ₂₅ , R ₂₆ , and R ₂₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a fluorine atom.
A ₂ to A ₄ independently represent -C (= O)-or -S (= O) _2-.
At _{least two of R 25} , R ₂₆ , and R ₂₇ may be combined with each other to form a ring.

[4]
The pattern forming method according to any one of [1] to [3], wherein the Onishi parameter of the polymer (A) is 4.2 or less.
[5]
The pattern forming method according to any one of [1] to [4], wherein the polymer (A) has two or more repeating units having a hydrophilic group, and the repeating units are different from each other.
[6]
The pattern forming method according to [5], wherein the polymer (A) has three or more types of repeating units having a hydrophilic group, and the repeating units are different from each other.

[7]
The pattern forming method according to any one of [1] to [6], wherein the repeating unit having a hydrophilic group includes a repeating unit having a carboxy group or a hydroxyl group.
[8]
The pattern forming method according to any one of [1] to [7], wherein the repeating unit having a hydrophilic group includes a repeating unit having a carboxy group.
[9]
The pattern forming method according to any one of [1] to [8], wherein the polymer (A) has at least one repeating unit having a carboxy group and one or more repeating units having a hydroxyl group.

[10]
The pattern forming method according to [9], wherein the repeating unit having a carboxy group is a repeating unit represented by the following general formula (1).

In the above general formula (1),
R ₃₁ represents a hydrogen atom or an alkyl group.
A ₃₁ represents a single bond or a (r + 1) valent linking group.
Y represents a carboxy group.
r represents an integer of 1 or more.

[11]
The pattern forming method according to [9] or [10], wherein the repeating unit having a hydroxyl group is a repeating unit represented by the following general formula (2).

In the above general formula (2),
R ₄₁ represents a hydrogen atom or an alkyl group.
A ₄₁ represents a single bond or (s + 1) valent linking group. However, A ₄₁ does not have an aromatic ring.
Z represents a hydroxyl group.
s represents an integer of 1 or more.

[12]
The pattern forming method according to any one of [1] to [11], wherein the weight average molecular weight of the polymer (A) is 7,000 or less.
[13]
The pattern forming method according to any one of [1] to [12], wherein the weight average molecular weight of the polymer (A) is 6000 or less.

[14]
The pattern forming method according to any one of [1] to [13], wherein the photoacid generator (B) is a mixture of two compounds represented by the following general formula (ZI-3).

In the above general formula (ZI-3),
R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkenyl group.
R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or an aryl group. R ₂ and R ₃ may be connected to each other to form a ring.
R ₁ and R ₂ may be connected to each other to form a ring.
_RX and _Ry independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group. .. _RX and R _y may be linked to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, and an amide bond.
Z ⁻ represents an anion represented by any of the following general formulas (A1) to (A3).

[15]
The photoacid generator (B) is a mixture of two compounds represented by the general formula (ZI-3), and two acids are generated by irradiation with active light or radiation, and these two acids are generated. The pattern forming method according to [14], wherein the acid dissociation constant pKa value at 25 ° C. differs by 0.5 or more.

[16]
Any of [1] to [15], wherein the content of the photoacid generator (B) is 6% by mass or less based on the total solid content of the actinic cheilitis or radiation-sensitive resin composition. The pattern forming method according to item 1.

[17]
The actinic light-sensitive or radiation-sensitive resin composition contains (D) an acid diffusion control agent, and the content of the (D) acid diffusion control agent is higher than the content of the (B) photoacid generator. The pattern forming method according to any one of [1] to [16], wherein the molar ratio is 0.40 or less.

[18]
The pattern forming method according to any one of [1] to [17], wherein the developer is an alkaline developer.
[19]
A method for manufacturing an electronic device, which comprises the pattern forming method according to any one of [1] to [18].

[20]
(I) A step of forming an actinic cheilitis or radiation-sensitive film having a film thickness of 700 nm or more with an actinic cheilitis or radiation-sensitive resin composition.
(Ii) A step of irradiating the above-mentioned sensitive light-sensitive or radiation-sensitive film with active light or radiation having a wavelength of 200 nm or less, and
(Iii) A step of developing a sensitive light-sensitive or radiation-sensitive film irradiated with active light or radiation having a wavelength of 200 nm or less using a developing solution.
A sensitive light-sensitive or radiation-sensitive resin composition used in a pattern forming method having the above.
The actinic light-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-degradable group and (B) a photoacid generator.
The polymer (A) has a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8000 or less.

According to the present invention, when a pattern is formed from a thick film (having a thickness of 700 nm or more), an actinic light-sensitive radiation-sensitive film, the resolution is excellent, and cracks in the resist pattern and peeling of the resist pattern are prevented. It is possible to provide a pattern forming method using a suppressable actinic or radiation-sensitive resin composition, a method for producing an electronic device, and an actinic or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having 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). Further, the "organic group" in the present specification means a group containing at least one carbon atom.

Further, in the present specification, the type of the substituent, the position of the substituent, and the number of the substituents when "may have a substituent" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and for example, the following substituent T can be selected.

(Substituent T)
Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy group such as methoxy group, ethoxy group and tert-butoxy group; aryloxy group such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and metoxalyl group and the like. Acrylic groups of: alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; Carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; formyl group ; And combinations of these.

As used herein, the term "active light" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB). : Electron Beam) and the like. As used herein, the term "light" means active light or radiation.
Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, EUV light, etc., but also electron beams, and the term "exposure". It also includes drawing with particle beams such as ion beams.
In the present specification, "-" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

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

In the present specification, the amount of each component in the composition is the total amount of the plurality of applicable substances present in the composition unless otherwise specified, when a plurality of the substances corresponding to each component are present in the composition. means.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
As used herein, the term "total solid content" refers to the total mass of the components excluding the solvent from the total composition of the composition. Further, the "solid content" is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
In the present specification, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[Pattern formation method]
The pattern forming method of the present invention will be described.

The pattern forming method of the present invention
(I) A step of forming a sensitive light-sensitive or radiation-sensitive film having a film thickness of 700 nm or more by a sensitive light-sensitive or radiation-sensitive resin composition (film formation step).
(Ii) A step (exposure step) of irradiating the above-mentioned sensitive light-sensitive or radiation-sensitive film with active light or radiation having a wavelength of 200 nm or less, and
(Iii) A step of developing a sensitive light or radiation sensitive film irradiated with active light or radiation having a wavelength of 200 nm or less using a developing solution (development step).
It is a pattern forming method having
The actinic light-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-degradable group and (B) a photoacid generator.
The polymer (A) has a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8000 or less, which is a pattern forming method.

According to such a configuration, when a pattern is formed from a thick film (having a thickness of 700 nm or more), a light-sensitive radiation-sensitive film, the resolution is excellent, and cracks and a resist pattern in the resist pattern are formed. Peeling can be suppressed.
The mechanism by which the present invention can exert the above effects is not always clear, but the present inventors consider it as follows.

First, in the step (ii) of the pattern forming method of the present invention, the active light or radiation having a wavelength of 200 nm or less is irradiated to the sensitive light or radiation sensitive film. Thereby, the resolvability of the obtained pattern can be made excellent.
The sensitive light-sensitive or radiation-sensitive resin composition used in the step (i) of the pattern forming method of the present invention contains (A) a polymer having an acid-degradable group and (B) a photoacid generator. The polymer (A) has a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8000 or less.

Conventionally, a resist film that irradiates active light or radiation (for example, ArF light) having a wavelength of 200 nm or less is generally a thin film (typically less than 700 nm), and in order to secure the strength of the film itself, the film is used. The weight average molecular weight of the resin is typically around 10,000 (for example, more than 8,000 to 12,000 or less) for the purpose of increasing the glass transition temperature (Tg) of the resin contained in the resist composition for forming the resin. There was a tendency. By using such a resin, it was possible to suppress the diffusion of acid even in a thin film and improve the resolution.
When it was examined to use a thick film (700 nm or more) as the resist film, cracks and peeling occurred in the resist film (and thus the resist pattern). When the weight average molecular weight of the resin is 9000 or more, the present inventors cannot withstand the stress in pattern formation as the thickness of the film becomes 700 nm or more, and cracks or peeling of the pattern occur. It has been found that it is necessary to further reduce the weight average molecular weight of the resin in view of the above stress.
However, even if the weight average molecular weight of the resin is further reduced, it is difficult to improve cracks and pattern peeling, and by further reducing the weight average molecular weight, excellent resolution cannot be obtained. rice field.
Further, as a result of diligent studies, the present inventors have found that the polymer (A) has a repeating unit having a hydrophilic group and the weight average molecular weight of the polymer (A) is 8000 or less. As for the film, it has been found that the resist film (and thus the resist pattern) can reduce cracks and peeling and improve the resolution.
Since the polymer (A) has a hydrophilic group, it can interact with the acid generated in the exposed portion and suppress the diffusion of the acid in the unexposed portion, so that the film is thick. Nevertheless, it is probable that the resolution was excellent.
Further, by strengthening the strength of the film itself by the interaction between the hydrophilic groups of the polymer (A), the weight average molecular weight can be lowered while the weight average molecular weight can be reduced, and the weight average molecular weight can be further increased. By setting the value to 8000 or less, it is considered that the thick film can be less affected by stress, and cracks and peeling of the resist pattern can be suppressed in the resist film (and thus the resist pattern).
Further, when the polymer (A) has a hydrophilic group, the interaction with the substrate is increased, and the adhesion to the resist film tends to be improved.

As described above, in the step (ii) of the pattern forming method of the present invention, the active light or radiation having a wavelength of 200 nm or less is irradiated to the sensitive light or radiation sensitive film, and is used in the pattern forming method of the present invention. The polymer (A) contained in the sensitive light-sensitive or radiation-sensitive composition has a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8000 or less. Therefore, surprisingly, when a pattern is formed from a thick film (having a thickness of 700 nm or more), a light-sensitive radiation-sensitive film, the resolution is excellent, and cracks and resist patterns in the resist pattern are formed. It is probable that the peeling could be suppressed.

[Actinic cheilitis or radiation-sensitive resin composition]
The actinic light-sensitive or radiation-sensitive resin composition used in the step (i) of the pattern forming method will be described.

The actinic light-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-degradable group and (B) a photoacid generator.
The polymer (A) has a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8000 or less.

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

<(A) Polymer>
The sensitive light-sensitive or radiation-sensitive resin composition of the present invention is a polymer having an acid-degradable group, the polymer has a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer is It contains 8000 or more polymers (also referred to as "(A) polymer" or "polymer (A)").
In this case, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer. A negative pattern is preferably formed.

(Repeating unit with hydrophilic group)
The polymer (A) has a repeating unit having a hydrophilic group.
The hydrophilic group is not particularly limited as long as it is a group having an affinity for water, and for example, a group having a carboxy group, a hydroxyl group, a lactone group, a sulton group, a cyano group, a sulfonamide group, or an ester group (provided that the group has an ester group). , The ester group does not form a ring).
The repeating unit having a hydrophilic group preferably contains a repeating unit having a carboxy group or a hydroxyl group.

It is particularly preferable that the repeating unit having a hydrophilic group includes a repeating unit having a carboxy group. Since the carboxy group has strong hydrophilicity and the interaction between the carboxy group and other hydrophilic groups becomes stronger, the effect of the present invention can be further enhanced.
It is particularly preferable that the polymer (A) has a repeating unit having a carboxy group.

The repeating unit having a carboxy group is not particularly limited, but is preferably a repeating unit represented by the following general formula (1).

The alkyl group of R ₃₁ is not particularly limited, but an alkyl group having 1 to 4 carbon atoms is preferable. The alkyl group of R ₃₁ may have a substituent, and examples of the substituent include the above-mentioned substituent T.

In _{the (r + 1) valent linking group of A 31,} the divalent linking group when r is 1 is not particularly limited, but is an alkylene group, a cycloalkylene group, an aromatic group, -CO-, -COO-, Alternatively, a group consisting of a combination of two or more of these can be mentioned.
The alkylene group may be linear or branched, preferably having 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms.
The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms.
The aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, and further preferably an aromatic group having 6 to 15 carbon atoms.
The aromatic ring constituting the aromatic group is not particularly limited, and examples thereof include an aromatic ring having 6 to 20 carbon atoms, and specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a thiophene ring. can. It is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

The alkylene group, cycloalkylene group, and aromatic group may further have a substituent. The further substituent is not particularly limited, but the above-mentioned substituent T is preferable.

As a specific example of the (r + 1) -valent linking group when r is an integer of 2 or more, (r-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of the divalent linking group. Can be preferably mentioned.
The (r + 1) -valent linking group may further have a substituent.

r represents an integer of 1 or more. In addition, r represents the number of Y.
The upper limit of r is not particularly limited, but is preferably an integer of 9 or less.
r is preferably an integer of 1 to 5, and more preferably an integer of 1 to 2.

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

The repeating unit having the above hydroxyl group is not particularly limited, but is preferably a repeating unit represented by the following general formula (2).

The alkyl group of R ₄₁ is not particularly limited, but is preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group of R ₄₁ may have a substituent, and examples of the substituent include the above-mentioned substituent T.

The (s + 1) valent linking group of A ₄₁ is not particularly limited as a divalent linking group when s is 1, but an alkylene group, a cycloalkylene group, -CO-, -COO-, or these can be used. A group consisting of a combination of two or more can be mentioned.
The alkylene group may be linear or branched, preferably having 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms.
The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms.

The alkylene group and the cycloalkylene group may further have a substituent. The further substituent is not particularly limited, but the above-mentioned substituent T is preferable.

As a specific example of the (s + 1) -valent linking group when s is an integer of 2 or more, (s-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of the divalent linking group. Can be preferably mentioned.
The (s + 1) valence linking group may further have a substituent.
Note that A ₄₁ does not have an aromatic ring.

s represents an integer of 1 or more. In addition, s represents the number of Z.
The upper limit of s is not particularly limited, but is preferably an integer of 6 or less.
s is preferably an integer of 1 to 5, and more preferably an integer of 1 to 2.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (2) will be given below, but the present invention is not limited to these specific examples.

The lactone group and sultone group are described below.
As the lactone group or sultone group, any one having a lactone structure or a sultone structure can be used, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable, and 5 to 7 members. A bicyclo structure or a spiro structure formed on a member ring lactone structure and another ring structure is condensed, or a bicyclo structure or a spiro structure is formed on a 5 to 7 member ring sultone structure. Is more preferable. 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). It is more preferred to have a repeating unit. Further, the lactone structure or the 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), (SL1-1).

The lactone-structured portion or the sultone-structured portion may or may not have a _{substituent (Rb 2).} Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-degradable group and the like. More preferably, it is an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of existing substituents (Rb ₂ ) may be bonded to each other to form a ring.

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

In the above general formula (III),
A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).
n is the _{number of repetitions of the structure represented by −R 0} −Z−, represents an integer of 0 to 5, is preferably 0 or 1, and more preferably 0. When n is 0, -R _0- Z- does not exist and a single bond is formed.
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. When _{there are a plurality of R 0} , each 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) will be given below, but the present invention is not limited to these specific examples. _{The following specific example corresponds to the case where R 7} in the general formula (III)) is a methyl group, but R ₇ can be arbitrarily substituted with a hydrogen atom, a halogen atom, or a monovalent organic group. ..

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

The sulfonamide group is a group represented by -SO ₂ NR ₅₁ R ₅₂ . R ₅₁ and R ₅₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
The alkyl group as R ₅₁ and R ₅₂ is not particularly limited, but may be linear or branched, and an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Alkyl groups 1 to 4 are more preferred.
The cycloalkyl group as R ₅₁ and R ₅₂ is not particularly limited, but may be monocyclic or polycyclic, a cycloalkyl group having 3 to 15 carbon atoms is preferable, and a cycloalkyl group having 3 to 10 carbon atoms is more preferable. A cycloalkyl group having 3 to 6 carbon atoms is more preferable.
The aryl group as R ₅₁ and R ₅₂ is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 15 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. ..

The alkyl group, cycloalkyl group, and aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

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

A group having an ester group (however, the ester group does not form a ring) (hereinafter, also simply referred to as a "group having an ester group") is a group having an ester group (-COO-). However, the ester group does not form a ring.
The ester group in the group having an ester group does not directly bond to the main chain of the polymer (A).

The group having an ester group is not particularly limited, but -COO-R ₆₁ or -OCO-R ₆₂ is preferable. R ₆₁ and R ₆₂ each independently represent an alkyl group, a cycloalkyl group, or an aryl group.

The alkyl group as R ₆₁ and R ₆₂ is not particularly limited, but may be linear or branched, and an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Alkyl groups 1 to 4 are more preferred.
The cycloalkyl group as R ₆₁ and R ₆₂ is not particularly limited, but may be monocyclic or polycyclic, a cycloalkyl group having 3 to 15 carbon atoms is preferable, and a cycloalkyl group having 3 to 10 carbon atoms is more preferable. A cycloalkyl group having 3 to 6 carbon atoms is more preferable.
The carbon constituting the cycloalkyl group (carbon contributing to ring formation) may be a carbonyl carbon or may be replaced with a hetero atom (for example, an oxygen atom or a sulfur atom).
In a preferred embodiment, one carbon constituting the cycloalkyl group (carbon contributing to ring formation) is a carbonyl carbon, and another carbon constituting the cycloalkyl group (carbon contributing to ring formation) is replaced with a heteroatom. Is preferable.

The aryl group as R ₆₁ and R ₆₂ is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 15 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. ..

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

The repeating unit having a hydrophilic group may have one hydrophilic group or may have a plurality of hydrophilic groups. The repeating unit having a hydrophilic group preferably has 1 to 8 hydrophilic groups, more preferably 1 to 4 groups, and further preferably 1 to 2 hydrophilic groups. It is most preferable to have one. When the repeating unit having a hydrophilic group has a plurality of hydrophilic groups, the plurality of hydrophilic groups may be the same or different.

The repeating unit having a hydrophilic group may have an acid-degradable group. The acid-degradable groups are as described below. When the repeating unit having a hydrophilic group has an acid-degradable group, the repeating unit having a hydrophilic group also corresponds to the repeating unit having an acid-degradable group described later.
The repeating unit having a hydrophilic group preferably does not have an acid-degradable group.

The content of the repeating unit having a hydrophilic group contained in the polymer (A) (the total of a plurality of repeating units having a hydrophilic group) is 10 to 10 to all the repeating units of the polymer (A). 80 mol% is preferable, 20 to 70 mol% is more preferable, and 30 to 70 mol% is further preferable.

The content of the repeating unit having a carboxy group contained in the polymer (A) (the total of a plurality of repeating units having a carboxy group) is 1 to 1 to all the repeating units of the polymer (A). 30 mol% is preferable, 5 to 25 mol% is more preferable, and 5 to 20 mol% is further preferable.
Further, the content of the repeating unit having a carboxy group contained in the repeating unit having a hydrophilic group of the polymer (A) (the total of a plurality of repeating units having a carboxy group) has all the hydrophilic groups. With respect to the repeating unit, 1 to 40 mol% is preferable, 1 to 30 mol% is more preferable, and 1 to 20 mol% is further preferable.

(Repeating unit with acid-degradable group)
The polymer (A) preferably has a repeating unit having an acid-degradable group.

The acid-degradable group preferably has a structure in which the polar group is protected by a group (leaving group) that is decomposed and eliminated by the action of an acid.
Examples of the polar group include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkylcarbonyl). Imid group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) methylene Examples thereof include acidic groups such as groups (typically, groups dissociating in a 2.38 mass% tetramethylammonium hydroxide aqueous solution), alcoholic hydroxyl groups and the like.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than the hydroxyl group directly bonded on the aromatic ring (phenolic hydroxyl group), and the α-position of the hydroxyl group is electron attraction such as a fluorine atom. Excludes aliphatic alcohol groups substituted with sex groups (eg, hexafluoroisopropanol groups, etc.). 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 an acid-degradable group is a group in which the hydrogen atom of these groups is replaced with a group (leaving group) that is eliminated by the action of an acid.
Examples of the group (leaving group) desorbed by the action of acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and-. C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and the like can be mentioned.
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be combined with each other to form a ring.
R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are not particularly limited, but alkyl groups having 1 to 8 carbon atoms are preferable, and for example, methyl group, ethyl group, propyl group, n-butyl group and sec- Butyl group, hexyl group, octyl group and the like can be mentioned.
The cycloalkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is not particularly limited, but a cycloalkyl group having 3 to 8 carbon atoms is preferable, 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. Groups, androstanyl groups and the like can be mentioned. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
The aryl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is not particularly limited, but an aryl group having 6 to 10 carbon atoms is preferable, 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 not particularly limited, but an aralkyl group having 7 to 12 carbon atoms is preferable, 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 not particularly limited, but an alkenyl group having 2 to 8 carbon atoms is preferable, and for example, a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group and the like can be used. Can be mentioned.
The _{ring formed by bonding R 36} and R ₃₇ to 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-degradable group, a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group and the like are preferable, and an acetal group or a tertiary alkyl ester group is more preferable.

The polymer (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 independently represent an alkyl group or a cycloalkyl group, respectively.
Any two of Rx ₁ to Rx ₃ may or may not be combined to form a ring structure.

Examples of the divalent linking group of T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group or an arylene group.
T is preferably single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and 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 groups of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. Groups, t-butyl groups and the like are preferably mentioned. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may have a part of the carbon-carbon bond as a double bond.
Examples _{of the cycloalkyl group of 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, and an adamantyl group. The polycyclic cycloalkyl group of is preferred.

The _{ring structure formed by combining Rx 1} , Rx ₂ and Rx ₃ is a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, or a norbornane ring or a tetracyclo. Polycyclic cycloalkyl rings such as decane rings, tetracyclododecane rings, and adamantane rings are preferred. A cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable. As _{the ring structure formed by combining Rx 1} , Rx ₂ and Rx ₃ , the structure shown below is also preferable.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (AI) will be 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 the general formula (AI) is a methyl group, but Xa ₁ can be arbitrarily substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

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

Further, the polymer (A) is decomposed as a repeating unit having an acid-degradable group by the action of an acid described in paragraphs [0363] to [0364] of US Patent Application Publication No. 2016/0070167A1 to form an alcohol. It may have a repeating unit containing a group that produces a sex hydroxyl group.

The repeating unit having an acid-decomposable group may have the above-mentioned hydrophilic group. When the repeating unit having an acid-degradable group has the above-mentioned hydrophilic group, the repeating unit having an acid-degradable group also corresponds to the repeating unit having a hydrophilic group.

The polymer (A) may contain a repeating unit having an acid-decomposable group alone or in combination of two or more.

The content of the repeating unit having an acid-degradable group contained in the polymer (A) (the total of a plurality of repeating units having an acid-degradable group) is based on all the repeating units of the polymer (A). It is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol%.

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

In addition, as a specific example of the repeating unit having neither an acid-degradable group nor a hydrophilic group, the repeating unit disclosed in paragraph [0433] of U.S. Patent Application Publication No. 2016/0070167A1 can be mentioned. Can be done.
The polymer (A) may contain a repeating unit having neither an acid-decomposable group nor a hydrophilic group alone or in combination of two or more.
The content of the repeating unit having neither an acid-decomposable group nor a hydrophilic group is preferably more than 0 to 50 mol%, preferably more than 0 to 30 mol%, based on all the repeating units in the polymer (A). More preferably, more than 0 to 20 mol% is further preferable.

In addition to the above-mentioned repeating structural units, the polymer (A) has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general necessary properties of resist such as resolution, heat resistance, and sensitivity. It can have various repeating structural units for regulatory purposes. 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 acid esters, methacrylic acid 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 the monomers corresponding to the various repeating structural units may be copolymerized.
In the polymer (A), the molar ratio of each repeating unit is appropriately set in order to adjust various performances.

The Onishi parameter of the polymer (A) is not particularly limited, but is preferably 4.2 or less, more preferably 3.9 or less, and further preferably 3.7 or less.
When the value of the Onishi parameter of the polymer (A) is reduced, the carbon density becomes high. By setting the value of the Onishi parameter to 4.2 or less, it is possible to obtain a high carbon density while having a hydrophilic group. The hydrophobicity of the resist film is increased, and in a hydrophobic field such as when the resist film is exposed, the diffusion of acid to the unexposed area due to exposure is further suppressed by the hydrophilic group, and the developability is further improved. Can be considered.
Further, the presence of the hydrophilic group in such a hydrophobic field makes the effect of hydrophilicity relatively large, and cracks in the resist pattern and peeling of the resist pattern can be further suppressed.
The lower limit of the Onishi parameter of the polymer (A) is not particularly limited, but is preferably 2.0 or more.

The Onishi parameter of the polymer (A) can be measured as follows.
When the polymer (A) has only one type of repeating unit, the Onishi parameter of the monomer corresponding to the repeating unit becomes the Onishi parameter of the polymer (A).
The Onishi parameter is a parameter commonly used to express carbon density and can be calculated by the following equation (H. Goken, S. Esho, Y. Ohnishi, J. Electrochem. Soc., 130, 423. (1983)).
Onishi parameter = (total number of atoms in the monomer) / [(number of carbon atoms in the monomer)-(number of oxygen atoms in the monomer)]

When the polymer (A) has two or more types of repeating units, the Onishi parameter of the monomer corresponding to each repeating unit is obtained by the above method, and each of the Onishi parameters of each monomer is used. The sum of the values obtained by multiplying the content (% by mass) in the polymer (A) of the repeating unit and dividing by 100 was used as the Onishi parameter of the polymer (A).

When the polymer (A) has a repeating unit 1, a repeating unit 2 ... a repeating unit X, the Onishi parameter of the polymer (A) is calculated from the following formula (1).

Onishi parameter of polymer (A) = N ₁ (Onishi parameter of monomer corresponding to repeating unit 1) × W ₁ (content rate of repeating unit 1 (mass%)) / 100 + N ₂ (corresponding to repeating unit 2) Ohnishi parameter) × _{W 2} (the content of the repeating unit 2 (wt%) of monomer) / 100+ · · · N _X (Ohnishi parameter of the monomer corresponding to the repeating unit X) × _{W X} (repeating units X Content rate (mass%)) / 100 ... (1)

The method for setting the Onishi parameter of the polymer (A) to 4.2 or less is not particularly limited, but one preferred embodiment is that the polymer (A) contains a repeating unit having a high carbon density such as adamantane. Be done.

It is preferable that the polymer (A) has two or more repeating units having a hydrophilic group, and the repeating units are different from each other.
As a result, when a pattern is formed from a thick film sensitive light-sensitive radiation film, the resolution is further excellent, and cracks in the resist pattern and peeling of the resist pattern can be further suppressed.
Further, it is preferable that the polymer (A) has three or more kinds of repeating units having a hydrophilic group, and the repeating units are different from each other.
The repeating unit having a hydrophilic group preferably contains a repeating unit having a carboxy group or a hydroxyl group.
Further, it is particularly preferable that the repeating unit having a hydrophilic group includes a repeating unit having a carboxy group.

It is preferable that the polymer (A) has at least one repeating unit having a carboxylic acid group and one or more repeating units having a hydroxyl group.
It is preferable that the repeating unit having the carboxylic acid group is the repeating unit represented by the general formula (1).
Further, it is preferable that the repeating unit having a hydroxyl group is the repeating unit represented by the general formula (2).

When the composition of the present invention is for ArF exposure, it is preferable that the polymer (A) has substantially no aromatic group from the viewpoint of the transparency of ArF light. More specifically, among all the repeating units of the polymer (A), the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, which is ideal. Is more preferably 0 mol%, i.e. not having a repeating unit having an aromatic group. Further, the polymer (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

It is preferable that all the repeating units of the polymer (A) are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate-based repeating units, all of the repeating units are acrylate-based repeating units, and all of the repeating units are either methacrylate-based repeating units or acrylate-based repeating units. Although it can be used, it is preferable that the acrylate-based repeating unit is 50 mol% or less with respect to all the repeating units of the polymer (A).

The weight average molecular weight of the polymer (A) is 8,000 or less.
The polymer (A) has a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is set to 8,000 or less to form a pattern from a thick film sensitive light-sensitive radiation-sensitive film. In this case, the resolution is further excellent, and cracks in the resist pattern and peeling of the resist pattern can be further suppressed.
On the other hand, if the weight average molecular weight of the polymer (A) exceeds 8,000, the above effect cannot be achieved, and when a pattern is formed from a thick film sensitive light-sensitive radiation-sensitive film, a resist pattern is formed. It becomes difficult to suppress cracks and peeling of the resist pattern in the above.

The weight average molecular weight of the polymer (A) is preferably 7,000 or less, and more preferably 6,000 or less.
The lower limit of the weight average molecular weight of the polymer (A) is not particularly limited, but is preferably 1,000 or more.
The dispersity (Mw / Mn) of the polymer (A) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and 1.1. ~ 2.0 is more preferable.

The polymer (A) may be used alone or in combination of two or more.
The content of the polymer (A) in the total solid content of the composition of the present invention is generally 50.0% by mass or more. 60.0% by mass or more is preferable, 70.0% by mass or more is more preferable, and 80.0% by mass or more is further preferable. The upper limit is not particularly limited, but 99.8% by mass or less is preferable, 99.5% by mass or less is more preferable, and 99.2% by mass or less is further preferable.

<(B) Photoacid generator>
The composition of the present invention contains a photoacid generator (hereinafter, also referred to as "photoacid generator (B)").
A photoacid generator is a compound that generates an acid when irradiated with active light or radiation.
As the photoacid generator, a compound that generates an organic acid by irradiation with active light or radiation is preferable. For example, a sulfonium salt compound, an iodonium salt compound, a diazonium salt compound, a phosphonium salt compound, an imide sulfonate compound, an oxime sulfonate compound, a diazodisulfone compound, a disulfone compound, and an o-nitrobenzyl sulfonate compound can be mentioned.

As the photoacid generator, a known compound that generates an acid by irradiation with active light or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs [0125]-[0319] of U.S. Patent Application Publication No. 2016/0070167A1, paragraphs [0083]-[0094] of U.S. Patent Application Publication No. 2015/0004544A1, U.S. Patent Application Publication No. 2016/0237190A1. The known compounds disclosed in paragraphs [0323] to [0402] of the specification can be suitably used as the photoacid generator (B).

Preferable embodiments of the photoacid generator (B) include, for example, compounds represented by the following general formulas (ZI), (ZII) and (ZIII).

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

Preferable embodiments of the cation in the general formula (ZI) include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.
The photoacid generator (B) 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 via a linking group.

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

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

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group (for example, carbon number of carbon atoms). 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 used as a substituent.

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

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

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

The alkyl group as R ₁ is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and 1 to 10 carbon atoms. Alkyl groups of are more preferred.
The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The cycloalkyl group as R ₁ is not particularly limited, but may be monocyclic or polycyclic, a cycloalkyl group having 3 to 20 carbon atoms is preferable, a cycloalkyl group having 3 to 15 carbon atoms is more preferable, and a cycloalkyl group having 3 to 15 carbon atoms is more preferable. A cycloalkyl group of ~ 10 is more preferred.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The alkoxy group as R ₁ is not particularly limited, but an alkoxy group having 1 to 20 carbon atoms is preferable, an alkoxy group having 1 to 15 carbon atoms is more preferable, and an alkoxy group having 1 to 10 carbon atoms is further preferable.
The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The cycloalkoxy group as R ₁ is not particularly limited, but a cycloalkoxy group having 3 to 20 carbon atoms is preferable, a cycloalkoxy group having 3 to 15 carbon atoms is more preferable, and a cycloalkoxy group having 3 to 10 carbon atoms is further preferable. preferable.
The cycloalkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The aryl group as R ₁ is not particularly limited, but may be monocyclic or polycyclic, and an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 15 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is preferable. Aryl groups are more preferred.
The aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T, but an alkoxy group is preferable.

The alkenyl group as R ₁ is not particularly limited, but an alkenyl group having 1 to 20 carbon atoms is preferable, an alkenyl group having 1 to 15 carbon atoms is more preferable, and an alkenyl group having 1 to 10 carbon atoms is further preferable.
The alkenyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

R ₁ is preferably an aryl group.

The alkyl group as R ₂ and R ₃ is not particularly limited, but may be linear or branched, and an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 15 carbon atoms is more preferable, and an alkyl group having 1 to 15 carbon atoms is more preferable. Alkyl groups from 1 to 10 are more preferred.
The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The cycloalkyl group as R ₂ and R ₃ is not particularly limited, but may be monocyclic or polycyclic, a cycloalkyl group having 3 to 20 carbon atoms is preferable, and a cycloalkyl group having 3 to 15 carbon atoms is more preferable. A cycloalkyl group having 3 to 10 carbon atoms is more preferable.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The aryl groups as R ₂ and R ₃ are not particularly limited, but may be monocyclic or polycyclic, and an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 15 carbon atoms is more preferable, and an aryl group having 6 to 15 carbon atoms is more preferable. Aryl groups of ~ 10 are more preferred.
The aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The alkoxy groups as R ₂ and R ₃ are not particularly limited, but an alkoxy group having 1 to 20 carbon atoms is preferable, an alkoxy group having 1 to 15 carbon atoms is more preferable, and an alkoxy group having 1 to 10 carbon atoms is further preferable. ..
The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The cycloalkoxy groups as R ₂ and R ₃ are not particularly limited, but a cycloalkoxy group having 3 to 20 carbon atoms is preferable, a cycloalkoxy group having 3 to 15 carbon atoms is more preferable, and a cycloalkoxy group having 3 to 10 carbon atoms is preferable. Groups are even more preferred.
The cycloalkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

R ₂ and R ₃ are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an alkoxy group, and more preferably a hydrogen atom or an alkyl group.

R ₂ and R ₃ may be connected to each other to form a ring, and examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and a 5- or 6-membered ring. More preferred.
Further, R ₁ and R ₂ may be connected to each other to form a ring, and the ring structure may include a 3 to 10-membered ring, preferably a 4- to 8-membered ring, and a 5- or 6-membered ring. Is more preferable.

_{The alkyl groups as RX} and R _y are not particularly limited, but may be linear or branched, and an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 15 carbon atoms is more preferable, and an alkyl group having 1 to 15 carbon atoms is more preferable. Alkyl groups from 1 to 10 are more preferred.
The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The cycloalkyl group as R _X and R _y is not particularly limited, may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms is more preferable.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

Alkenyl group as R _X and R _y is not particularly limited, preferably an alkenyl group having 1 to 20 carbon atoms, more preferably an alkenyl group having 1 to 15 carbon atoms, more preferably an alkenyl group having 1 to 10 carbon atoms ..
The alkenyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The aryl group as R _X and R _y is not particularly limited, may be monocyclic or polycyclic, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, 6 carbon atoms Aryl groups of ~ 10 are more preferred.
The aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

_{The 2-oxoalkyl groups as RX} and _Ry are not particularly limited, but 2-oxoalkyl having 1 to 20 carbon atoms is preferable, 2-oxoalkyl group having 1 to 15 carbon atoms is more preferable, and 1 to 15 carbon atoms are more preferable. 10 2-oxoalkyl is more preferred.
The 2-oxoalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

_{The 2-oxocycloalkyl group as RX} and _Ry is not particularly limited, but a 2-oxocycloalkyl group having 3 to 20 carbon atoms is preferable, and a 2-oxocycloalkyl group having 3 to 15 carbon atoms is more preferable. , A 2-oxocycloalkyl group having 3 to 10 carbon atoms is more preferable.
The 2-oxocycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

Alkoxycarbonylalkyl group as R _X and R _y is not particularly limited, preferably an alkoxycarbonyl group having 3 to 22 carbon atoms, more preferably an alkoxycarbonyl group having 3 to 17 carbon atoms, 3 to 12 carbon atoms Alkoxycarbonylalkyl groups of are more preferred.
The alkoxycarbonylalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

Alkoxycarbonyl cycloalkyl group as R _X and R _y is not particularly limited, preferably an alkoxycarbonyl cycloalkyl group having 5 to 24 carbon atoms, more preferably an alkoxycarbonyl cycloalkyl group having 5 to 19 carbon atoms, carbon atoms 5-14 alkoxycarbonylcycloalkyl groups are more preferred.
The alkoxycarbonylcycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

_RX and R _y may be linked to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, and an amide bond.
The ring structure preferably contains an oxygen atom.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings in which two or more of these rings are combined. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

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

The alkyl group as R ₁₃ is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and 1 to 10 carbon atoms. Alkyl groups of are more preferred.
The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The cycloalkyl group as R ₁₃ is not particularly limited, but may be monocyclic or polycyclic, a cycloalkyl group having 3 to 20 carbon atoms is preferable, a cycloalkyl group having 3 to 15 carbon atoms is more preferable, and a cycloalkyl group having 3 to 15 carbon atoms is more preferable. A cycloalkyl group of ~ 10 is more preferred.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The alkoxy group as R ₁₃ is not particularly limited, but an alkoxy group having 1 to 20 carbon atoms is preferable, an alkoxy group having 1 to 15 carbon atoms is more preferable, and an alkoxy group having 1 to 10 carbon atoms is further preferable.
The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The alkoxycarbonyl group as R ₁₃ is not particularly limited, but an alkoxycarbonyl group having 2 to 21 carbon atoms is preferable, an alkoxycarbonyl group having 2 to 16 carbon atoms is more preferable, and an alkoxycarbonyl group having 2 to 11 carbon atoms is further preferable. preferable.
The alkoxycarbonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The alkyl group as R ₁₄ is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and 1 to 10 carbon atoms. Alkyl groups of are more preferred.
The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The cycloalkyl group as R ₁₄ is not particularly limited, but may be monocyclic or polycyclic, a cycloalkyl group having 3 to 20 carbon atoms is preferable, a cycloalkyl group having 3 to 15 carbon atoms is more preferable, and a cycloalkyl group having 3 to 15 carbon atoms is more preferable. A cycloalkyl group of ~ 10 is more preferred.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The alkoxy group as R ₁₄ is not particularly limited, but an alkoxy group having 1 to 20 carbon atoms is preferable, an alkoxy group having 1 to 15 carbon atoms is more preferable, and an alkoxy group having 1 to 10 carbon atoms is further preferable.
The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The alkoxycarbonyl group as R ₁₄ is not particularly limited, but an alkoxycarbonyl group having 2 to 21 carbon atoms is preferable, an alkoxycarbonyl group having 2 to 16 carbon atoms is more preferable, and an alkoxycarbonyl group having 2 to 11 carbon atoms is further preferable. preferable.
The alkoxycarbonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The _{alkylcarbonyl group as R 14} is not particularly limited, but an alkylcarbonyl group having 2 to 21 carbon atoms is preferable, an alkylcarbonyl group having 2 to 16 carbon atoms is more preferable, and an alkylcarbonyl group having 2 to 11 carbon atoms is further preferable. preferable.
The alcoholylcarbonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The alkylsulfonyl group as R ₁₄ is not particularly limited, but an alkylsulfonyl group having 1 to 20 carbon atoms is preferable, an alkylsulfonyl group having 1 to 15 carbon atoms is more preferable, and an alkylsulfonyl group having 1 to 10 carbon atoms is further preferable. preferable.
The alkylsulfonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The cycloalkylsulfonyl group as R ₁₄ is not particularly limited, but a cycloalkylsulfonyl group having 3 to 20 carbon atoms is preferable, a cycloalkylsulfonyl group having 3 to 15 carbon atoms is more preferable, and a cycloalkylsulfonyl group having 3 to 10 carbon atoms is more preferable. A sulfonyl group is more preferred.
The cycloalkylsulfonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

R ₁₄ is, if there are two or more, plural R ₁₄ may being the same or different.

The alkyl group as R ₁₅ is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and 1 to 10 carbon atoms. Alkyl groups of are more preferred.
The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The cycloalkyl group as R ₁₅ is not particularly limited, may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, 3 carbon atoms A cycloalkyl group of ~ 10 is more preferred.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

The naphthyl group as R ₁₅ may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

Bonded to two R ₁₅ each other may form a ring. When two R ₁₅ are combined to form a ring together, the ring structure is an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
The ring structure preferably contains an oxygen atom.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings in which two or more of these rings are combined. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

In a preferred embodiment, two R ₁₅ is an alkyl group, it is preferable to form a ring structure.

Next, the general formulas (ZII) and (ZIII) will be described.
In the general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
As _{the aryl group of R 204} to R _207, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group of 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, etc.). Butyl group and pentyl group), cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) can be mentioned.

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

It is preferable that the photoacid generator (B) contains a compound represented by the general formula (ZI-3) or a compound represented by the general formula (ZI-4).
By using such a compound, the transparency of the resist film is increased, so that even more excellent resolution can be obtained particularly when exposed with ArF light.

Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^- is not particularly limited, it is preferably an anion represented by any one of the following formulas (A1) ~ (A3).
^{Further, Z −} in the general formula (ZI-3) ^{or X −} in the general formula (ZI-4) is not particularly limited, but is represented by any of the following general formulas (A1) to (A3). It is preferably an anion.
^{It is preferable that Z −} in the general formula (ZI-3) ^{and X −} in the general formula (ZI-4) are anions represented by any of the following general formulas (A1) to (A3).

The alkyl groups as R ₂₁ and R ₂₂ are not particularly limited, but may be linear or branched, and an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Alkyl groups 1 to 4 are more preferred.
The cycloalkyl group as R ₂₁ and R ₂₂ is not particularly limited, but may be monocyclic or polycyclic, a cycloalkyl group having 3 to 15 carbon atoms is preferable, and a cycloalkyl group having 3 to 10 carbon atoms is more preferable. A cycloalkyl group having 3 to 6 carbon atoms is more preferable.
The _{alkyl group substituted with a fluorine atom as R 21} and R ₂₂ is specifically 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.
The _{cycloalkyl group substituted with a fluorine atom as R 21} and R ₂₂ is specifically a cycloalkyl 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, the cycloalkyl group, the alkyl group substituted with the fluorine atom, and the cycloalkyl group substituted with the fluorine atom may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.
At _{least one of R 21} and R ₂₂ is a fluorine atom, an alkyl group substituted with a fluorine atom, and a cycloalkyl group substituted with a fluorine atom.

Examples of the divalent linking group of L include -COO- (-C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, and -S-. , -SO-, -SO _2- , alkylene group (preferably 1 to 6 carbon atoms), cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene group (preferably 2 to 6 carbon atoms) and a plurality of these. Examples thereof include a divalent linking group in which the above are combined.
Among these, an alkylene group, -COO -, - OCO -, - CONH -, - NHCO -, - CO -, - O -, - SO 2 -, - SO 2 - alkylene group -, - COO- alkylene group - , -Alkylene group-COO-, -OCO-alkylene group-, -alkylene group-OCO-, -CONH-alkylene group-or -NHCO-alkylene group-is preferable, and alkylene group, -COO-, -OCO-,- CONH-, -SO _2- , -COO-alkylene group-, -alkylene group-COO-, -OCO-alkylene group- or -alkylene group-OCO- are more preferable.
The alkylene group, cycloalkylene group, and alkenylene group may have a substituent.
It may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T, and a fluorine atom is preferable.

X represents an organic group.
The number of carbon atoms of the organic group is not particularly limited, but is generally 1 to 30, preferably 1 to 20.
The organic group is not particularly limited, and examples thereof include an alkyl group and an alkoxy group.
The alkyl group is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. More preferred.
The alkoxy group is not particularly limited, but an alkoxy group having 1 to 10 carbon atoms is preferable, an alkoxy group having 1 to 6 carbon atoms is more preferable, and an alkoxy group having 1 to 4 carbon atoms is further preferable.
The alkyl group and the alkoxy group may have a substituent. It may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T, and a fluorine atom is preferable.

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

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

The cyclic organic group may have a substituent. The substituent may be, for example, an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms) and a cycloalkyl group (which may be monocyclic, polycyclic or spirocyclic). Often, 3 to 20 carbon atoms are preferable), an aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid. Examples include ester groups. The carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be carbonyl carbon.

The alkyl group as R ₂₃ is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and 1 to 4 carbon atoms. Alkyl groups of are more preferred.
The cycloalkyl group as R ₂₃ is not particularly limited, but may be monocyclic or polycyclic, a cycloalkyl group having 3 to 15 carbon atoms is preferable, a cycloalkyl group having 3 to 10 carbon atoms is more preferable, and a cycloalkyl group having 3 to 10 carbon atoms is more preferable. Cycloalkyl groups of ~ 6 are more preferred.
The alkyl group and the cycloalkyl group may have a substituent. It may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T, and a fluorine atom is preferable.

R _x represents an organic group.
The organic group as R _{x is the same} as the organic group described as X above.

The alkyl group as R _{24 is the same} as the alkyl group described as R ₂₃ above.
The cycloalkyl group as R _{24 is the same} as the cycloalkyl group described as R ₂₃ above.
A ₁ represents -C (= O)-or -S (= O) _2- . As A ₁ , -S (= O) ₂ -is preferable.

R ₂₃ and R ₂₄ may be coupled to each other to form a ring. When two R ₁₅ are combined to form a ring together, the ring structure is an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, an amide bond or a sulfonyl bond.
Examples of the ring structure include a non-aromatic heterocycle and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

The alkyl groups as R ₂₅ , R ₂₆ , and R _{27 are the same} as the alkyl groups described as R ₂₃ above.
The cycloalkyl groups as R ₂₅ , R ₂₆ , and R _{27 are the same} as the cycloalkyl groups described as R ₂₃ above.
A ₂ to A ₄ independently represent -C (= O)-or -S (= O) _2-. It is preferable that A ₂ to A ₄ represent −S (= O) _2−.

At _{least two of R 25} , R ₂₆ , and R ₂₇ may be combined with each other to form a ring. When _{at least two of R 25} , R ₂₆ , and R ₂₇ are bonded to each other to form a ring, this ring structure forms an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, an amide bond, and a sulfonyl bond. It may be included.
Examples of the ring structure include a non-aromatic hydrocarbon ring, a non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

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

Anion in formula (ZI), the general formula (ZII) Z ^-, Z in the general formula (ZI-3) ^-, and the general formula X in (ZI-4) ^- shows the preferred embodiment below.

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

In addition, the following photoacid generators can also be preferably used. Bu represents a butyl group.

The photoacid generators (PAG-A to PAG-Z, PAG-AA to PAG-AK) used in the examples can also be preferably used.

The photoacid generator may be in the form of a small molecule compound or may be incorporated in a part of the polymer. Further, the form of the small molecule compound and the form incorporated in a part of the polymer may be used in combination.
The photoacid generator is preferably in the form of a small molecule compound.
When the photoacid generator is in the form of a small molecule compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.
When the photoacid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above, or may be incorporated in a resin different from the resin (A). ..
The photoacid generator may be used alone or in combination of two or more.
The content of the photoacid generator in the composition (the total of a plurality of types, if present) is preferably 0.1 to 35% by mass, preferably 0.5 to 25% by mass, based on the total solid content of the composition. Is more preferable, 0.8 to 15% by mass is further preferable, and 1 to 10% by mass is particularly preferable.
As a preferred embodiment, the content of the photoacid generator in the composition (the total of a plurality of types, if present) is preferably 6% by mass or less, preferably 5% by mass or less, based on the total solid content of the composition. More preferred.

As a preferred embodiment, it is preferable to use two or more photoacid generators in combination.
The photoacid generator (B) is preferably a mixture of two compounds represented by the following general formula (ZI-3).

Each group in the cation portion of the above general formula (ZI-3) is as described above.
The anions represented by any of the above general formulas (A1) to (A3) as ^{Z − are as described above.}

As a preferred embodiment, when two kinds of photoacid generators are used in combination and two kinds of acids are generated by irradiation with active light or radiation, the acid dissociation constant pKa values of these two kinds of acids are different by 0.5 or more. It is preferable that the difference is 1.0 or more, more preferably 1.5 or more, and even more preferably 1.5 or more.

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in, for example, Chemical Handbook (II) (Revised 4th Edition, 1993, edited by Japan Chemical Society, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be 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 Hammett's substituent constants and values based on a database of publicly known literature values. All the values of pKa described in the present specification indicate the values obtained by calculation using the following software package 1.
Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

In a preferred embodiment, the photoacid generator (B) is a mixture of two compounds represented by the general formula (ZI-3), and two acids are generated by irradiation with active light or radiation. The acid dissociation constant pKa values of these two acids at 25 ° C. are preferably different by 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more.
Further, the acid dissociation constant pKa value of the acid generated from the photoacid generator at 25 ° C. by irradiation with active light or radiation preferably satisfies pKa <-1, and more preferably pKa <-3.

<Acid diffusion control agent (D)>
The composition of the present invention preferably contains an acid diffusion control agent (D). The acid diffusion control agent (D) acts as a quencher that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-degradable resin in the unexposed portion due to the excess generated acid. .. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation, an onium salt (DC) which is a relatively weak acid with respect to an acid generator, and a nitrogen atom. A low molecular weight compound (DD) having a group having a group desorbed by the action of an acid, an onium salt compound (DE) having a nitrogen atom in the cation portion, or the like can be used as an acid diffusion control agent. In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0995] to [0187] of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1. The known compounds disclosed in paragraphs [0403] to [0423] of the specification and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 are preferably used as the acid diffusion control agent (D). can.

As the basic compound (DA), preferably, a compound having a structure represented by the following formulas (A) to (E) can be mentioned.

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

The alkyl groups in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
Regarding the above alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
It is more preferable that the alkyl groups in the general formulas (A) and (E) are unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidin, pyrazole, pyrazoline, piperazin, aminomorpholine, aminoalkylmorpholin, piperidine and the like are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, etc. 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, and the like are more preferable.

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

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

Preferred partial structures of the proton acceptor functional group include, for example, crown ethers, aza-crown ethers, primary to tertiary amines, pyridines, imidazoles, and pyrazine structures.

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

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

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

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

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

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

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

An onium salt (DC), which is a weak acid relative to an acid generator, is a compound having a cation moiety and an anion moiety in the same molecule, and the cation moiety and anion moiety are linked by a covalent bond ( Hereinafter, it may also be referred to as “compound (DCA)”).
The compound (DCA) is preferably a compound represented by any 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 one or more carbon atoms.
L ₁ represents a divalent linking group or a single bond that links the cation site and the anion site.
-X ^- ^_is, -COO ^-, ^-SO 3 - represents an anion portion selected from -R ₄ ^-, -SO ₂ -, and ^-N. R ₄ is a linking site with the adjacent N atom, a carbonyl group (-C (= O) -) , sulfonyl group _{(-S (= O) 2 -} ), and sulfinyl group (-S (= O) - ) Represents a monovalent substituent having at least one of them.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be combined with each other to form a ring structure. Further, in the general formula (C-3), two of R ₁ to R ₃ are combined to represent one divalent substituent, which may be bonded to an N atom by a double bond.

Substituents having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino. Examples thereof include a carbonyl group and an arylaminocarbonyl group. It is preferably an alkyl group, a cycloalkyl group, or an aryl group.

_{L 1} as a divalent linking group includes a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two kinds thereof. Examples thereof 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 of these.

A small molecule compound (DD) having a nitrogen atom and having a group desorbed by the action of an acid (hereinafter, also referred to as “compound (DD)”) has a group desorbed by the action of an acid on the nitrogen atom. It is preferably an amine derivative having.
As the group desorbed by the action of the acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminoal ether group is preferable, and a carbamate group or a hemiaminol ether group is more preferable. ..
The molecular weight of compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

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

As Rb, a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
Examples of the ring formed by connecting the two Rbs to each other include an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon and a derivative thereof.
Specific structures of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph [0466] of the US Patent Publication No. US2012 / 0135348A1. ..

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

In the general formula (6)
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may be interconnected to form a heterocycle with the nitrogen atom in the equation. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in the above general formula (d-1), and the same applies to preferred examples.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra are independently substituted with the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb, respectively. As a good group, it may be substituted with a group similar to the group described above.

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

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

A preferable example of the acid diffusion control agent (D) is shown below.

Quencher-A to Quencher-K used in the examples can also be preferably used.

In the composition of the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more.
The content of the acid diffusion control agent (D) in the composition (the total of a plurality of types, if present) is preferably 0.01 to 10% by mass, preferably 0.05 to 10% by mass, based on the total solid content of the composition. 5% by mass is more preferable. The content of the acid diffusion control agent (D) in the composition (the total of a plurality of types if present) is the content of the photoacid generator (B) in the composition (if a plurality of types are present, the total thereof). In terms of molar ratio, 0.40 or less is preferable, 0.30 or less is more preferable, and 0.25 or less is further preferable.

<Hydrophobic resin (E)>
The composition of the present invention may contain a hydrophobic resin (E) different from the polymer (A).
By containing the hydrophobic resin (E) in the composition of the present invention, it is possible to control the static / dynamic contact angle on the surface of the sensitive light-sensitive or radiation-sensitive film. This makes it possible to improve development characteristics, suppress outgas, improve immersion liquid followability in immersion exposure, reduce immersion defects, and the like.
The hydrophobic resin (E) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and a polar / non-polar substance is used. It does not have to contribute to uniform mixing.

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

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

The hydrophobic resin (E) preferably has at least one group selected from the following groups (x) to (z).
(X) Acid group (y) A group that decomposes by the action of an alkaline developer and increases its solubility in an alkaline developer (hereinafter, also referred to as a polarity converting group).
(Z) A group that decomposes by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonyl group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkyl). Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) ) Methylene groups and the like can be mentioned.
As the acid group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonimide group, or a bis (alkylcarbonyl) methylene group is preferable.

Examples of the group (y) that decomposes due to the action of the alkaline developing solution and increases the solubility in the alkaline developing solution include a lactone group, a carboxylic acid ester group (-COO-), and an acid anhydride group (-C (O) OC). (O)-), acidimide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate ester group (-OC (O) O-), sulfate ester group (-OSO ₂ O-), and Examples thereof include a sulfonic acid ester group (-SO ₂ O-), and a lactone group or a carboxylic acid ester group (-COO-) is preferable.
The repeating unit containing these groups is a repeating unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include a repeating unit made of an acrylic acid ester and a methacrylic acid ester. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced into the end of the resin by using a polymerization initiator or chain transfer agent having these groups at the time of polymerization.
Examples of the repeating unit having a lactone group include the same repeating units having the lactone structure described above in the section of resin (A).

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

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

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

On the other hand, especially if the hydrophobic resin (E) comprises a CH ₃ partial structure side chain moiety, a hydrophobic resin (E) is a form that does not contain a fluorine atom and a silicon atom substantially also preferred. Further, it is preferable that the hydrophobic resin (E) is substantially composed of only repeating units composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably more than 8,000 to 100,000, more preferably more than 8,000 to 50,000.

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

As the hydrophobic resin (E), a known resin can be appropriately selected and used alone or as a mixture thereof. For example, the known resins disclosed in paragraphs [0451]-[0704] of U.S. Patent Application Publication 2015 / 0168830A1 and paragraphs [0340]-[0356] of U.S. Patent Application Publication 2016 / 0274458A1 are hydrophobic. It can be suitably used as the sex resin (E). The repeating unit disclosed in paragraphs [0177] to [0258] of US Patent Application Publication No. 2016/0237190A1 is also preferable as the repeating unit constituting the hydrophobic resin (E).

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

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

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

As the organic solvent, a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group may be used may be used.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplified compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether is preferable. (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. Further, as the solvent containing no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl Ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, Cyclopentanone or 2-heptanone is more preferred. Propylene carbonate is also preferable as the solvent containing no hydroxyl group.
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 containing no hydroxyl group is preferable in terms of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

<Surfactant (H)>
The composition of the present invention may or may not contain a surfactant. When a surfactant is contained, a fluorine-based and / or a silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) ) Is preferable.

By containing a surfactant in the composition of the present invention, it is possible to obtain a resist pattern having good sensitivity and resolution and few adhesions and development defects when an exposure light source of 250 nm or less, particularly 220 nm or less is used. can.
Examples of the fluorine-based and / or silicon-based surfactants include the 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, preferably 0.0005 to 1% by mass, based on 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 uneven distribution of the surface of the hydrophobic resin is increased. As a result, the surface of the sensitive light-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability during immersion exposure is improved.

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

The film thickness of the actinic light-sensitive film or the radiation-sensitive film (typically, the resist film) formed from the composition of the present invention is 700 nm or more.
The upper limit of the film thickness is not particularly limited, but is usually 10 μm.
The film thickness is preferably 700 to 5000 nm, more preferably 700 to 3000 nm, and even more preferably 700 to 2000 nm.
Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coatability or film forming property.
The solid content concentration of the composition of the present invention is usually 8 to 40% by mass, preferably 10 to 30% by mass, and more preferably 12 to 25% by mass. The solid content concentration is the mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.

The composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering the mixture, and then applying the above-mentioned components 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 even more preferably 0.03 μm or less. When the solid content concentration of the composition is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, still more preferably 0.3 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Laid-Open No. 2002-62667), cyclic filtration may be performed, and a plurality of types of filters may be arranged in series or in parallel. It may be connected to and filtered. Moreover, the composition may be filtered a plurality of times. Further, the composition may be degassed before and after the filter filtration.

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

The pattern forming method of the present invention is as described above.
(I) A step of forming a sensitive light-sensitive or radiation-sensitive film having a film thickness of 700 nm or more by a sensitive light-sensitive or radiation-sensitive resin composition (film formation step).
(Ii) A step (exposure step) of irradiating the above-mentioned sensitive light-sensitive or radiation-sensitive film with active light or radiation having a wavelength of 200 nm or less, and
(Iii) A step of developing a sensitive light or radiation sensitive film irradiated with active light or radiation having a wavelength of 200 nm or less using a developing solution (development step).
Have.

The pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii) above, and may further include the following steps.
In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be immersion exposure.
The pattern forming method of the present invention preferably includes (iv) preheating (PB: PreBake) step before the (ii) exposure step.
The pattern forming method of the present invention preferably includes (v) post-exposure heating (PEB: Post Exposure Bake) step after the (ii) exposure step and before the (iii) development step.
The pattern forming method of the present invention may include (ii) exposure steps a plurality of times.
The pattern forming method of the present invention may include (iv) a preheating step a plurality of times.
The pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.
(I) The film forming step is specifically a step of forming a sensitive light-sensitive or radiation-sensitive film having a film thickness of 700 nm or more on the support by using the sensitive light-sensitive or radiation-sensitive resin composition.

In the pattern forming method of the present invention, the above-mentioned (i) film forming step, (ii) exposure step, and (iii) developing step can be performed by a generally known method.
Further, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), antireflection film) is formed between the sensitive light-sensitive or radiation-sensitive film and the support. You may. As the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (top coat) may be formed on the upper layer of the sensitive light-sensitive or radiation-sensitive film. As the protective film, a known material can be appropriately used. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/02444438 and International Patent Application Publication No. 2016/157988A can be preferably used. The composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent.
A protective film may be formed on the upper layer of the sensitive light-sensitive or radiation-sensitive film containing the above-mentioned hydrophobic resin.

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

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

The light source wavelength used in the exposure process is 200 nm or less. Thereby, the resolvability of the obtained pattern can be made excellent. On the other hand, when the light source wavelength exceeds 200 nm, a pattern having a desired resolution cannot be obtained in a thick film.
As the light source, if the light source wavelength is 200nm or less, in particular, without limitation, specifically, ArF excimer laser (193 nm), _{F 2} excimer laser (157 nm), X-ray, EUV (13 nm), or electron beam Is preferable, and ArF excimer laser, EUV or electron beam is more preferable.

In the (iii) developing step, the developing solution may be an alkaline developing solution or a developing solution containing an organic solvent (hereinafter, also referred to as an organic developing solution), but an alkaline developing solution is preferable.

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

The organic developer is a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. It is preferable to have it.

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

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

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

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass or less, based on the total amount of the developing solution. 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, if necessary.

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

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

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

A step of developing with an alkaline aqueous solution (alkaline developing step) and a step of developing with a developer containing an organic solvent (organic solvent developing step) may be combined. As a result, the pattern can be formed without dissolving only the region having an intermediate exposure intensity, 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 step or the rinsing step, a process of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be added. Further, after the rinsing treatment or the treatment with the supercritical fluid, a heat treatment may be performed to remove the water remaining in the pattern.

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

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

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

The rinse liquid may contain an appropriate amount of a surfactant.
In the rinsing step, the substrate developed with an organic developer is washed with a rinsing solution containing an organic solvent. The cleaning treatment method is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (rotary coating method), or a method of immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinse liquid on the substrate surface (spray method), or the like can be applied. Above all, it is preferable to perform the cleaning treatment by the rotary coating method, and after cleaning, rotate the substrate at a rotation speed of 2,000 to 4,000 rpm to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. By this heating step, 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 sensitive light-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developing solution, a rinsing solution, an antireflection film forming composition, or The composition for forming a top coat, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt or less, further preferably 10 ppt or less, and substantially not contained (below the detection limit of the measuring device). Is particularly preferable.

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

In order to prevent contamination of the above-mentioned various materials, US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351), Japanese Patent It is preferably stored in the container described in Application Publication No. 2017-13804 (Japanese Patent Laid-Open No. 2017-13804) and the like.

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. Examples of the method for improving the surface roughness of the pattern include a method of treating a resist pattern with a plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/010497. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. A known method as described in 8328 83280N-1 “EUV Resist Curing Technology for LWR Reduction and Etch Sensitivity Enhancement” may be applied.
Further, the resist pattern formed by the above method is a spacer disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Application Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/209941. It can be used as a core material (Core) for the process.

In the present invention, the aspect ratio of the cross-sectional shape from the thick film sensitive light-sensitive radiation film (the ratio of the line width of the space pattern to the film thickness of the resist pattern, that is, (thickness of the resist pattern) / (line of the space pattern) It is preferable to form a pattern having a very high width)).
The aspect ratio is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
The upper limit is not particularly limited, but is, for example, 30 or less.
The formed resist pattern can be used for implant applications.
Further, the formed resist pattern can be used for etching.

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

[Actinic cheilitis or radiation-sensitive resin composition]
In addition, the present invention
(I) A step of forming an actinic cheilitis or radiation-sensitive film having a film thickness of 700 nm or more with an actinic cheilitis or radiation-sensitive resin composition.
(Ii) A step of irradiating the above-mentioned sensitive light-sensitive or radiation-sensitive film with active light or radiation having a wavelength of 200 nm or less, and
(Iii) A step of developing a sensitive light-sensitive or radiation-sensitive film irradiated with active light or radiation having a wavelength of 200 nm or less using a developing solution.
A sensitive light-sensitive or radiation-sensitive resin composition used in a pattern forming method having the above.
The actinic light-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-degradable group and (B) a photoacid generator.
The polymer (A) also relates to a sensitive light-sensitive or radiation-sensitive resin composition having a repeating unit having a hydrophilic group and having a weight average molecular weight of the polymer (A) of 8000 or less.
The polymer (A) and the photoacid generator (B) are as described above.

Hereinafter, the present invention will be described in more detail based on Examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. The scope of the present invention is not construed as limiting by the examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

<Polymer (A)>
The structures of the polymers (A) used (Polymer-A to Polymer-V, Polymer-AA, Polymer-AB, and Polymer-AC) are shown below.
The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the polymer (A) were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (polystyrene equivalent). Is). The composition ratio (mol% ratio) of the polymer ^{was measured by 13} C-NMR (Nuclear Magnetic Resonance).
Although the polymers (Polymer-W to Polymer-Z) are not the polymer (A), they are described below for convenience.

<Photoacid generator (B)>
The structures of the photoacid generators (PAG-A to PAG-Z, PAG-AA to PAG-AK) used are shown below. The structure of the acid generated by each photoacid generator by irradiation with active light or radiation is shown in Table 1 below. Table 1 also shows the values of the acid dissociation constant pKa at 25 ° C. for each compound. pKa is a value calculated by using software package 1.
Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

The acid generated by PAG-A by irradiation with active light or radiation is the same as the acid generated by PAG-I to PAG-S and PAG-AA to PAG-AC by irradiation with active light or radiation.
The acid generated by PAG-B by irradiation with active light or radiation is the same as the acid generated by PAG-T by irradiation with active light or radiation.
The acid generated by PAG-C by irradiation with active light or radiation is the same as the acid generated by PAG-U, PAG-AD to PAG-AE by irradiation with active light or radiation.
The acid generated by PAG-D by irradiation with active light or radiation is the same as the acid generated by PAG-V by irradiation with active light or radiation.
The acid generated by PAG-E by irradiation with active light or radiation is the same as the acid generated by PAG-W and PAG-AF to PAG-AG by irradiation with active light or radiation.
The acid generated by PAG-F by irradiation with active light or radiation is the same as the acid generated by PAG-X by irradiation with active light or radiation.
The acid generated by PAG-G by irradiation with active light or radiation is the same as the acid generated by PAG-Y, PAG-AH to PAG-AI by irradiation with active light or radiation.
The acid generated by PAG-H by irradiation with active light or radiation is the same as the acid generated by PAG-Z and PAG-AJ to PAG-AK by irradiation with active light or radiation.

<Acid diffusion control agent (D)>
The structures of the acid diffusion control agents (D) (Quencher-A to Quencher-K) used are shown below.

The structures of the surfactants (Surfactant-A to Surfactant-D) used are shown below.

Surfactant-A: Megafuck R-41 (manufactured by DIC Corporation)

The solvent used is shown below.
PGMEA: Propylene Glycol Monomethyl Ether Acetate (PGMEA)
PGME: Propylene glycol monomethyl ether (PGME)
CyHx: Cyclohexanone EEP: Ethylethoxypropionate EL: Ethyl lactate GBL: Gamma-butyrolactone

<Preparation of Actinic Cheilitis or Radiation Sensitive Resin Composition> (ArF exposure)
(Examples 1 to 42, 44 to 99, Reference Example 1, Comparative Examples 2 to 4, 6 to 11, 13 to 14)
The various components shown in Table 2 were mixed and mixed so as to have the solid content concentration (mass%) shown in Table 2 to obtain a solution. The obtained liquid was filtered through a UPE (ultra high molecular weight polyethylene) filter having a pore size of 0.1 μm. The obtained actinic cheilitis or radiation-sensitive resin composition (resist composition) was used in Examples and Comparative Examples.
In the resist composition, in this example and this comparative example, the solid content means all components other than the solvent.
In the table, the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content. In addition, the content ratio (mass%) of the solvent used to the total solvent is shown in the table.
The Onishi parameters of the polymer (A) are also shown in Table 2. The Onishi parameter can be obtained by the above method.

<Pattern formation method (1): ArF exposure, alkaline aqueous solution development (positive)>
A film thickness targeting the resist composition prepared above without providing an antireflection layer on a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane (film thickness shown in Table 2). The coating was applied at a speed of 120 ° C. and baked (PBake; PB) for 60 seconds at a temperature of 120 ° C. to form an active light-sensitive or radiation-sensitive film (resist film) having each film thickness.
The space pattern width of the pattern formed after reduced projection exposure and development using an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193 nm, NA 0.50) on the wafer on which the resist film is formed (hereinafter, simply space). Pattern exposure was performed through a mask having a line-and-space pattern such that the width (also referred to as width) is 500 nm and the pitch width is 1500 nm. Then, it is baked at a temperature of 115 ° C. for 60 seconds (Post Exposure Bake; PEB), developed with 2.38% by mass of tetramethylammonium hydroxide aqueous solution (TMAHaq) for 30 seconds, rinsed with pure water, and then spin-dried. bottom. As a result, an isolated space pattern having a space width of 500 nm and a pitch width of 1500 nm was obtained.
By the above procedure, an evaluation pattern wafer having a substrate and a pattern formed on the surface of the substrate was obtained.

(Film thickness)
The formed actinic or radiation-sensitive film (resist film) was measured at 16 points in a circle at a position 10 cm from the center by VM-3210 (manufactured by SCREEN), and the average value was taken as the film thickness.

<Performance evaluation>
[Resolution]
At a space width of 500 nm and a pitch width of 1500 nm after reduced projection exposure, the mask size of the space width (light transmitting portion) is reduced from 500 nm, and the minimum value of the space width in which the space pattern is resolved is used as the resolving power. The resolution was evaluated.
A scanning electron microscope (SEM) (Hitachi 9380II) was used to measure the space pattern width. It was judged that the smaller the value, the better the resolution.

[Cracks in resist patterns and peeling of resist patterns]
The evaluation pattern wafer was observed with a defect evaluation device KLA2360 (manufactured by KLA), and the number of pattern cracks and pattern peeling formed in one shot (that is, a rectangle having a length of 12 mm and a width of 6 mm) was determined. It was confirmed by the defect evaluation device KLA2360.
The number of cracks and pattern peeling of the formed pattern is the total of the number of cracks of the formed pattern and the number of pattern peeling.

<Pattern formation method (2): ArF exposure, organic solvent development (negative)>
A film thickness targeting the resist composition prepared above without providing an antireflection layer on a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane (film thickness shown in Table 2). The coating was applied at a speed of 120 ° C. and baked (PBake; PB) for 60 seconds at a temperature of 120 ° C. to form an active light-sensitive or radiation-sensitive film (resist film) having each film thickness.
The space pattern width of the pattern formed after reduced projection exposure and development using an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193 nm, NA 0.50) on the wafer on which the resist film is formed (hereinafter, simply space). Pattern exposure was performed through a mask having a line-and-space pattern such that the width (also referred to as width) is 500 nm and the pitch width is 1500 nm. Then, it was baked at a temperature of 115 ° C. for 60 seconds (Post Exposure Bake; PEB), developed with nBA or MAK for 30 seconds, rinsed with pure water, and then spin-dried. As a result, an isolated space pattern having a space width of 500 nm and a pitch width of 1500 nm was obtained.
In addition, nBA represents n-butyl acetate, and MAK represents 2-heptanone (methylamyl ketone).
By the above procedure, an evaluation pattern wafer having a substrate and a pattern formed on the surface of the substrate was obtained.

The film thickness was measured in the same manner as above.

<Performance evaluation>
[Resolution]
At a space width of 500 nm and a pitch width of 1500 nm after reduced projection exposure, the mask size of the space width (light-shielding part) is reduced from 500 nm, and the minimum value of the space width in which the space pattern is resolved is used as the resolution. The image quality was evaluated.
A scanning electron microscope (SEM) (Hitachi 9380II) was used to measure the space pattern width. It was judged that the smaller the value, the better the resolution.

<Preparation of Actinic Cheilitis or Radiation Sensitive Resin Composition> (EUV exposure)
(Example 43)
The various components shown in Table 2 were mixed and mixed so as to have the solid content concentration (mass%) shown in Table 2 to obtain a solution. The obtained solution is first filtered through a polyethylene filter having a pore size of 50 nm, then a nylon filter having a pore diameter of 10 nm, and finally a polyethylene filter having a pore diameter of 3 nm. A product (resist composition) was prepared.
In the resist composition, in this example, the solid content means all components other than the solvent.
In the table, the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content. In addition, the content ratio (mass%) of the solvent used to the total solvent is shown in the table.
The Onishi parameters of the polymer (A) are also shown in Table 2. The Onishi parameter can be obtained by the above method.

<Pattern formation method (3): EUV exposure, alkaline development (positive)>
AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an underlayer film having a film thickness of 30 nm. The resist composition shown in the table was applied onto the resist composition and baked (PB) at 120 ° C. for 60 seconds to form a positive resist film having a film thickness of 700 nm.
The resist film was subjected to pattern irradiation using an EUV exposure apparatus (Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech). As the lectil, a mask having a line size of 40 nm and a line: space = 1: 1 was used.
The exposed resist film was baked (PEB) at 120 ° C. for 60 seconds, then developed with an aqueous solution of tetramethylammonium hydroxide (TMAH, 2.38% by mass) (TMAHaq) for 30 seconds, and then rinsed with pure water for 30 seconds. .. A silicon wafer was rotated at a rotation speed of 1500 rpm for 30 seconds and further baked at 90 ° C. for 60 seconds to obtain a line-and-space pattern having a pitch of 80 nm and a line width of 40 nm (space width of 40 nm).
By the above procedure, an evaluation pattern wafer having a substrate and a pattern formed on the surface of the substrate was obtained.

The film thickness was measured in the same manner as above.

<Performance evaluation>
[Resolution]
At a space width of 50 nm and a pitch width of 500 nm after reduced projection exposure, the mask size of the space width (light transmitting portion) is reduced from 50 nm, and the minimum value of the space width in which the space pattern is resolved is used as the resolving power. The resolution was evaluated.
A scanning electron microscope (SEM) (Hitachi 9380II) was used to measure the space pattern width. It was judged that the smaller the value, the better the resolution.

<Preparation of Actinic Cheilitis or Radiation Sensitive Resin Composition> (KrF exposure)
(Comparative Examples 1 and 5)
The various components shown in Table 2 were mixed and mixed so as to have the solid content concentration (mass%) shown in Table 2 to obtain a solution. The obtained liquid was filtered through a UPE (ultra high molecular weight polyethylene) filter having a pore size of 0.1 μm. The obtained actinic cheilitis or radiation-sensitive resin composition (resist composition) was used in Comparative Examples.
In the resist composition, in this comparative example, the solid content means all components other than the solvent.
In the table, the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content. In addition, the content ratio (mass%) of the solvent used to the total solvent is shown in the table.
The Onishi parameters of the polymer (A) are also shown in Table 2. The Onishi parameter can be obtained by the above method.

<Pattern formation method (4): KrF exposure, alkaline aqueous solution development (positive)>
In the pattern forming method (1), the exposure apparatus was replaced with an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193 nm, NA0.50), and a KrF excimer laser scanner (ASML, PAS5500 / 850C, NA = 0. A pattern is formed in the same manner as in the pattern forming method (1) except that 68, σ = 0.60, wavelength 248 nm), and an evaluation pattern wafer having a substrate and a pattern formed on the substrate surface is obtained. Obtained.

The film thickness was measured in the same manner as above.

<Performance evaluation>
The resolution, cracks in the resist pattern, and peeling of the resist pattern were evaluated in the same manner as in the above pattern forming method (1).

<Preparation of Actinic Cheilitis or Radiation Sensitive Resin Composition> (i-ray exposure)
(Comparative Example 12)
The various components shown in Table 2 were mixed and mixed so as to have the solid content concentration (mass%) shown in Table 2 to obtain a solution. The obtained liquid was filtered through a UPE (ultra high molecular weight polyethylene) filter having a pore size of 0.1 μm. The obtained actinic cheilitis or radiation-sensitive resin composition (resist composition) was used in Comparative Examples.
In the resist composition, in this comparative example, the solid content means all components other than the solvent.
In the table, the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content. In addition, the content ratio (mass%) of the solvent used to the total solvent is shown in the table.
The Onishi parameters of the polymer (A) are also shown in Table 2. Onishi parameters can be obtained by the above method.

<Pattern formation method (5): i-line exposure, alkaline aqueous solution development (positive)>
In the pattern forming method (1), an i-line excimer laser scanner (CANON FPA-3000i5 +, wavelength 365 nm) is used instead of the ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193 nm, NA0.50). A pattern was formed in the same manner as in the pattern forming method (1), except that a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

The film thickness was measured in the same manner as above.

Table 2 shows the obtained evaluation results. In addition, "crack in resist pattern and peeling of resist pattern" was described as "crack".

According to the results of Table 2, according to the pattern forming method of the present invention, when a pattern is formed from a thick film (having a thickness of 700 nm or more), a sensitive ray-sensitive radiation-sensitive film, the resolution is excellent and the pattern is formed. It can be seen that cracks in the resist pattern and peeling of the resist pattern can be suppressed.
Since Reference Example 1 was a thin film (500 nm), it was possible to suppress cracks and peeling of the resist pattern in the resist pattern while having excellent resolution when forming a pattern from the sensitive light-sensitive radiation-sensitive film. When the film thickness was 700 nm, the effect of the present invention could not be obtained as shown in Comparative Example 2.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on February 27, 2020 (Japanese Patent Application No. 2020-32445) and a Japanese patent application filed on August 14, 2020 (Japanese Patent Application No. 2020-136960). Its contents are included here as a reference.

Claims

(I) A step of forming an actinic cheilitis or radiation-sensitive film having a film thickness of 700 nm or more with an actinic cheilitis or radiation-sensitive resin composition.
(Ii) A step of irradiating the active light or radiation sensitive film with active light or radiation having a wavelength of 200 nm or less, and
(Iii) A step of developing a sensitive light-sensitive or radiation-sensitive film irradiated with active light or radiation having a wavelength of 200 nm or less using a developing solution.
It is a pattern forming method having
The actinic light-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-degradable group and (B) a photoacid generator.
A pattern forming method, wherein the polymer (A) has a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8000 or less.
The pattern forming method according to claim 1, wherein the (B) photoacid generator comprises a compound represented by the following general formula (ZI-3) or a compound represented by the following general formula (ZI-4).

In the above general formula (ZI-3),
R 1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkenyl group.
R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or an aryl group. R 2 and R 3 may be connected to each other to form a ring.
R 1 and R 2 may be connected to each other to form a ring.
RX and Ry independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group. .. RX and R y may be linked to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, and an amide bond.
Z - represents an anion.

In the general formula (ZI-4),
l represents an integer of 0 to 2.
r represents an integer from 0 to 8.
R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group.
R 14 represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a cycloalkylsulfonyl group. R 14 is, if there are two or more, plural R 14 may being the same or different.
Each of R 15 independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Bonded to two R 15 each other may form a ring. When two R 15 are combined to form a ring together, the ring structure is an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
X - represents an anion.
Wherein Z - or the wherein X - pattern forming method according to claim 2, wherein the anion represented by any one of the following formulas (A1) ~ (A3).

In the above general formula (A1),
R 21 and R 22 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom. However, at least one of R 21 and R 22 is a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom.
L represents a single bond or a divalent linking group.
X represents an organic group.
In the above general formula (A2),
R 23 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, -C (= O) -Rx, or -S (= O) 2- Rx. Rx represents an organic group.
R 24 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a fluorine atom.
A 1 represents -C (= O)-or -S (= O) 2- .
R 23 and R 24 may be coupled to each other to form a ring.
In the above general formula (A3),
R 25 , R 26 , and R 27 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a fluorine atom.
A 2 to A 4 independently represent -C (= O)-or -S (= O) 2-.
At least two of R 25 , R 26 , and R 27 may be combined with each other to form a ring.
The pattern forming method according to any one of claims 1 to 3, wherein the Onishi parameter of the polymer (A) is 4.2 or less.
The pattern forming method according to any one of claims 1 to 4, wherein the polymer (A) has two or more types of repeating units having a hydrophilic group, and the repeating units are different from each other.
The pattern forming method according to claim 5, wherein the polymer (A) has three or more types of repeating units having a hydrophilic group, and the repeating units are different from each other.
The pattern forming method according to any one of claims 1 to 6, wherein the repeating unit having a hydrophilic group includes a repeating unit having a carboxy group or a hydroxyl group.
The pattern forming method according to any one of claims 1 to 7, wherein the repeating unit having a hydrophilic group includes a repeating unit having a carboxy group.
The pattern forming method according to any one of claims 1 to 8, wherein the polymer (A) has at least one repeating unit having a carboxy group and one or more repeating units having a hydroxyl group.
The pattern forming method according to claim 9, wherein the repeating unit having a carboxy group is a repeating unit represented by the following general formula (1).

In the above general formula (1),
R 31 represents a hydrogen atom or an alkyl group.
A 31 represents a single bond or a (r + 1) valent linking group.
Y represents a carboxy group.
r represents an integer of 1 or more.
The pattern forming method according to claim 9 or 10, wherein the repeating unit having a hydroxyl group is a repeating unit represented by the following general formula (2).

In the above general formula (2),
R 41 represents a hydrogen atom or an alkyl group.
A 41 represents a single bond or (s + 1) valent linking group. However, A 41 does not have an aromatic ring.
Z represents a hydroxyl group.
s represents an integer of 1 or more.
The pattern forming method according to any one of claims 1 to 11, wherein the weight average molecular weight of the polymer (A) is 7,000 or less.
The pattern forming method according to any one of claims 1 to 12, wherein the weight average molecular weight of the polymer (A) is 6000 or less.
The pattern forming method according to any one of claims 1 to 13, wherein the (B) photoacid generator is a mixture of two compounds represented by the following general formula (ZI-3).

In the above general formula (ZI-3),
R 1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkenyl group.
R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or an aryl group. R 2 and R 3 may be connected to each other to form a ring.
R 1 and R 2 may be connected to each other to form a ring.
RX and Ry independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group. .. RX and R y may be linked to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, and an amide bond.
Z − represents an anion represented by any of the following general formulas (A1) to (A3).

In the above general formula (A1),
R 21 and R 22 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom. However, at least one of R 21 and R 22 is a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom.
L represents a single bond or a divalent linking group.
X represents an organic group.
In the above general formula (A2),
R 23 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, -C (= O) -Rx, or -S (= O) 2- Rx. Rx represents an organic group.
R 24 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a fluorine atom.
A 1 represents -C (= O)-or -S (= O) 2- .
R 23 and R 24 may be coupled to each other to form a ring.
In the above general formula (A3),
R 25 , R 26 , and R 27 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a fluorine atom.
A 2 to A 4 independently represent -C (= O)-or -S (= O) 2-.
At least two of R 25 , R 26 , and R 27 may be combined with each other to form a ring.
The photoacid generator (B) is a mixture of two compounds represented by the general formula (ZI-3), and two acids are generated by irradiation with active light or radiation, and these two acids are generated. The pattern forming method according to claim 14, wherein the acid dissociation constant pKa value at 25 ° C. is different by 0.5 or more.
Any one of claims 1 to 15, wherein the content of the photoacid generator (B) is 6% by mass or less based on the total solid content of the actinic light-sensitive or radiation-sensitive resin composition. The pattern forming method described in 1.
The actinic light-sensitive or radiation-sensitive resin composition contains (D) an acid diffusion control agent, and the content of the (D) acid diffusion control agent is relative to the content of the (B) photoacid generator. The pattern forming method according to any one of claims 1 to 16, wherein the molar ratio is 0.40 or less.
The pattern forming method according to any one of claims 1 to 17, wherein the developer is an alkaline developer.
A method for manufacturing an electronic device, which comprises the pattern forming method according to any one of claims 1 to 18.
(I) A step of forming an actinic cheilitis or radiation-sensitive film having a film thickness of 700 nm or more with an actinic cheilitis or radiation-sensitive resin composition.
(Ii) A step of irradiating the active light or radiation sensitive film with active light or radiation having a wavelength of 200 nm or less, and
(Iii) A step of developing a sensitive light-sensitive or radiation-sensitive film irradiated with active light or radiation having a wavelength of 200 nm or less using a developing solution.
A sensitive light-sensitive or radiation-sensitive resin composition used in a pattern forming method having the above.
The actinic light-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-degradable group and (B) a photoacid generator.
The (A) polymer has a repeating unit having a hydrophilic group, and the weight average molecular weight of the (A) polymer is 8000 or less, which is an actinic light-sensitive or radiation-sensitive resin composition.