WO2016136476A1

WO2016136476A1 - Pattern forming method, active light sensitive or radiation sensitive resin composition, active light sensitive or radiation sensitive film, method for manufacturing electronic device, and electronic device

Info

Publication number: WO2016136476A1
Application number: PCT/JP2016/053983
Authority: WO
Inventors: 修史平野; 暁高田
Original assignee: 富士フイルム株式会社
Priority date: 2015-02-27
Filing date: 2016-02-10
Publication date: 2016-09-01
Also published as: JPWO2016136476A1; TW201640226A; JP6476276B2

Abstract

Provided is a pattern forming method which comprises: a step for forming a film using an active light sensitive or radiation sensitive resin composition; a step for exposing the film to light; and a step for forming a negative pattern by developing the film after light exposure with use of a developer liquid that contains an organic solvent. The active light sensitive or radiation sensitive resin composition contains a resin (Ab) that comprises, as a repeating unit that is decomposed by the action of an acid and generates a polar group, at least a repeating unit represented by general formula (Ab1).

Description

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

The present invention relates to a pattern formation method using a developer containing an organic solvent, an actinic ray-sensitive property, or a photoluminescence process, which is suitably used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other photofabrication processes. The present invention relates to a radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a method for producing an electronic device using these, and an electronic device. More specifically, a pattern forming method using a developer containing an organic solvent, actinic ray sensitive or radiation sensitive, which can be suitably used for microfabrication of a semiconductor element using an electron beam or EUV light (wavelength: around 13 nm). The present invention relates to a photosensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a method for producing an electronic device using these, and an electronic device.

Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line, and further to KrF excimer laser light.

Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. In the exposure, the acid generator in the exposed area is decomposed to generate an acid, and the acid generated in the post-exposure baking (PEB) is a reaction catalyst. Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development. A positive-type image forming method using this chemical amplification mechanism is currently mainstream (see, for example, Patent Documents 1 to 3).

On the other hand, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Accordingly, the exposure wavelength tends to be shortened, and at present, a positive image forming method using an electron beam, X-ray, or EUV light has been developed (for example, Patent Documents 4 to 9). See).

In recent years, a negative pattern forming method using a developer containing an organic solvent (hereinafter also referred to as “organic solvent developer”) is being developed (see, for example, Patent Document 10). According to this method, it is supposed that a highly accurate fine pattern can be stably formed.

JP-T-2004-504632 JP 2007-299002 A JP 11-352696 A JP 2007-248513 A JP 2007-248514 A JP 2007-206638 A JP 7-295221 A JP-A-6-161111 JP-A-2-25850 JP 2013-80004 A

As the miniaturization of the resist pattern is pursued, the pattern collapse is more likely to occur. From the viewpoint of preventing such pattern collapse, the resist film needs to be thinned. However, as the resist film becomes thinner as a result of pursuing miniaturization, a dilemma may occur that the resist film becomes less resistant to etching and cannot function as a resist film.

Thus, there is a trade-off between resist pattern miniaturization and etching resistance, and it is important how to satisfy this simultaneously.

In addition, in the positive type image forming method, although isolated lines can be formed relatively well, when a fine isolated space pattern with a narrow space width is formed, the pattern shape tends to deteriorate, for example, on the order of several tens of nm. Actually, it is difficult to form an isolated space pattern having a space width.

Furthermore, even in a negative type image forming method using an organic solvent developer, further improvement in performance is required for the resolution in forming an isolated space pattern.

The present invention has been developed in view of such circumstances, and is a pattern forming method capable of forming an isolated space pattern that is excellent in etching resistance and has a fine (for example, several tens of nm order), actinic ray sensitivity or It is an object to provide a radiation-sensitive resin composition and an actinic ray-sensitive or radiation-sensitive film.

The present invention also provides an electronic device manufacturing method and an electronic device using a pattern forming method that is excellent in etching resistance and can form a fine (for example, several tens of nm order) isolated space pattern. For the purpose.

In one aspect, the present invention is as follows.
[1]
An actinic ray-sensitive or radiation-sensitive resin containing at least a resin (Ab) containing a repeating unit represented by the following general formula (Ab1) as a repeating unit having a group that decomposes by the action of an acid to generate a polar group Forming a film using the composition;
Exposing the film; and
The pattern formation method including the process of developing the film | membrane after exposure using the developing solution containing an organic solvent, and forming a negative pattern.

Where
A ₁₁ represents a hydrogen atom or a substituent, A ₁₂ represents a single bond or a divalent aromatic ring group, A ₁₃ represents a hydrogen atom or a substituent, and L ₁₁ represents a single bond or a divalent group. Represents a linking group, R ₁₁ represents a group capable of leaving by the action of an acid, and r ₁₁ represents an integer of 1 or more.

However, at least one of A ₁₁ and A ₁₂ represents an aromatic ring group. When A ₁₂ is an aromatic ring group, L ₁₁ represents a divalent linking group, and an atom directly bonded to A ₁₂ in the linking group in this case is not an oxygen atom.

[2]
The pattern forming method according to [1], wherein the repeating unit represented by the general formula (Ab1) is a repeating unit represented by the following general formula (Ab2).

Where
R ₂₁ represents a group capable of leaving by the action of an acid, R ₂₂ represents a substituent, L ₂₁ represents a single bond or a divalent linking group, and p ₂₁ represents 0 or an integer of 1 or more. Q ₂₁ represents 0 or an integer of 1 or more.

[3]
The pattern forming method according to [1], wherein the repeating unit represented by the general formula (Ab1) is a repeating unit represented by the following general formula (Ab3).

Where
R ₃₁ represents a group capable of leaving by the action of an acid, R ₃₂ represents a substituent, L ₃₁ represents a divalent linking group, A ₃₁ represents a hydrogen atom or a substituent, and A ₃₃ Represents a hydrogen atom or a substituent, p ₃₁ represents 0 or an integer of 1 or more, q ₃₁ represents 0 or an integer of 1 or more, and r ₃₁ represents an integer of 1 or more.

However, in the divalent linking group represented by L ₃₁ , the atom directly bonded to the aromatic ring group in the formula is not an oxygen atom.

[4]
The pattern forming method according to any one of [1] to [3], wherein the resin (Ab) further has a repeating unit represented by the following general formula (A).

Where
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may form a ring with Ar ₄ or X _4, R ₄₂ in this case represents a single bond or an alkylene group.
X ₄ represents a single bond, an alkylene group, —COO—, or —CONR ₆₄ —. Here, R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond, —COO—, or an alkylene group.
Ar ₄ represents an (n + 1) -valent aromatic ring group, and when bonded to R ₄₂ to form a ring, represents an (n + 2) -valent aromatic ring group.
n represents an integer of 1 to 4.

[5]
In any one of [1] to [4], the group capable of leaving by the action of an acid represented by R ₁₁ in the general formula (Ab1) is a group represented by the following general formula (ALG1) or (ALG2) A pattern forming method according to any one of the above.

In general formula (ALG1),
R ₁ and R ₃ each independently represent a hydrogen atom or a substituent, and R ₂ represents a substituent. R ₁ and R ₂ may be bonded to each other to form a ring.
In general formula (ALG2),
R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group. Two selected from R ₄ , R ₅ and R ₆ may be bonded to each other to form a ring.

[6]
The pattern forming method according to any one of [1] to [5], wherein the exposure is exposure with an electron beam or extreme ultraviolet rays.

[7]
The pattern forming method according to any one of [1] to [6], wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a compound that generates an acid upon irradiation with actinic rays or radiation.

[8]
Forming a film using an actinic ray-sensitive or radiation-sensitive resin composition;
A step of exposing the film, and a step of developing the exposed film using a developer containing an organic solvent to form a negative pattern,
An actinic ray-sensitive or radiation-sensitive resin composition used in a pattern forming method comprising:
An actinic ray-sensitive or radiation-sensitive resin containing at least a resin (Ab) containing a repeating unit represented by the following general formula (Ab1) as a repeating unit having a group that decomposes by the action of an acid to generate a polar group Composition.

[9]
The actinic ray-sensitive or radiation-sensitive resin composition according to [8], wherein the repeating unit represented by the general formula (Ab1) is a repeating unit represented by the following general formula (Ab2).

[10]
The actinic ray-sensitive or radiation-sensitive resin composition according to [8], wherein the repeating unit represented by the general formula (Ab1) is a repeating unit represented by the following general formula (Ab3).

Where
R ₃₁ represents a group capable of leaving by the action of an acid, R ₃₂ represents a substituent, L ₃₁ represents a divalent linking group, p ₃₁ represents 0 or an integer of 1 or more, and A ₃₁ ₃₁ represents a hydrogen atom or a substituent, A ₃₃ represents a hydrogen atom or a substituent, q ₃₁ represents 0 or an integer of 1 or more, and r ₃₁ represents an integer of 1 or more.
However, in the divalent linking group represented by L ₃₁ , the atom directly bonded to the aromatic ring group in the formula is not an oxygen atom.

[11]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [8] to [10], wherein the resin (Ab) further has a repeating unit represented by the following general formula (A).

[12]
In any one of [8] to [11], the group capable of leaving by the action of an acid represented by R ₁₁ in the general formula (Ab1) is a group represented by the following general formula (ALG1) or (ALG2) The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1.

[13]
[13] An actinic ray-sensitive or radiation-sensitive film comprising the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [8] to [12].
[14]
[1] A method for manufacturing an electronic device including the pattern forming method according to any one of [7].
[15]
The electronic device manufactured by the manufacturing method of the electronic device as described in [14].

According to the present invention, a pattern forming method, an actinic ray-sensitive or radiation-sensitive resin composition, which has excellent etching resistance and can form a fine isolated space pattern on the order of several tens of nm, and an actinic ray-sensitive or It became possible to provide a radiation sensitive film. In addition, according to the present invention, there are provided an electronic device manufacturing method and an electronic device using a pattern forming method that has excellent etching resistance and can form a fine isolated space pattern on the order of several tens of nm. It has become possible.

In the description of a group (atomic group) in this specification, the notation that does not indicate substitution and non-substitution includes not only a substituent but also 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).

“Actinic ray” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet (EUV) ray, an X-ray or an electron beam (EB). Yes. In the present invention, “light” means actinic rays or radiation.

In addition, unless otherwise specified, “exposure” in the present invention is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays and EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
Hereinafter, embodiments of the present invention will be described in detail.

The pattern forming method of the present invention comprises:
Forming a film using an actinic ray-sensitive or radiation-sensitive resin composition;
Exposing the film,
The film after exposure is developed using a developer containing an organic solvent (organic solvent developer) to form a negative pattern.

In the following, first, the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter referred to as “the composition of the present invention”) used in the pattern forming method of the present invention will be described in detail, and then the present invention. Each process included in the pattern forming method will be described in detail.

<Actinic ray-sensitive or radiation-sensitive resin composition>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is negative-type development (when exposed, the solubility in the developer decreases, the exposed area remains as a pattern, and the unexposed area is removed. Development). That is, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition for organic solvent development used for development using an organic solvent developer. it can. Here, the term “for organic solvent development” means an application that is used in a step of developing using a developer containing at least an organic solvent.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, particularly a negative resist composition (that is, a resist composition for developing an organic solvent). It is preferable because a high effect can be obtained. The composition of the present invention is typically a chemically amplified resist composition.

[1] Resin (Ab)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (Ab) containing an acid-decomposable repeating unit. Accordingly, the resin (Ab) is a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid. Here, the acid-decomposable repeating unit is, for example, a group (hereinafter also referred to as “acid-decomposable group”) that decomposes into the main chain or side chain of the resin, or both the main chain and side chain by the action of an acid. ). The group generated by the decomposition is preferably a polar group, since the affinity with a developer containing an organic solvent is lowered and insolubilization or insolubilization (negative conversion) proceeds.

The resin (Ab) is at least a repeating unit represented by the following general formula (Ab1) (hereinafter also referred to as “repeating unit (Aba)”) as a repeating unit having a group that decomposes by the action of an acid to generate a polar group. .)including.

The general formula (Ab1) will be described in detail.
A ₁₁ represents a hydrogen atom or a substituent. Examples of the substituent represented by A ₁₁ include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aromatic ring group, and a hydroxy group. These groups excluding the hydroxy group may further have a substituent.

A ₁₂ represents a single bond or a divalent aromatic ring group, and at least one of A ₁₁ and A ₁₂ represents an aromatic ring group.

Examples of the aromatic ring group represented by A ₁₁ and A ₁₂ include an aromatic ring group having 6 to 18 carbon atoms (more preferably 6 to 10 carbon atoms) such as a benzene ring and a naphthalene ring, or a thiophene ring, furan, etc. Preferred examples include aromatic ring groups including heterocycles such as rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrrole rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, thiadiazole rings, and thiazole rings. More preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring group. These aromatic rings may have a substituent.

L ₁₁ represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L _11, an alkylene group, aromatic ring group, a cycloalkylene _{group, -COO-L 1 '-,} - O-L 1' -, - CONH-, these two or more And the like are formed by combining these groups. Here, L ₁ ′ represents an alkylene group (preferably having a carbon number of 1 to 20), a cycloalkylene group (preferably having a carbon number of 3 to 20), an aromatic ring group, or a combination of an alkylene group and an aromatic ring group.

The alkylene group as the divalent linking group represented by L ₁₁ is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group. . An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 or 2 carbon atoms is particularly preferable.

The cycloalkylene group as the divalent linking group represented by L ₁₁ is preferably a cycloalkylene group having 3 to 20 carbon atoms, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group. Group, cycloheptylene group, cyclooctylene group, norbornylene group or adamantylene group.

Specific examples of the definition and preferred range of the divalent aromatic ring group represented by L ₁₁ include the same specific examples as those given for the aromatic ring groups represented by A ₁₁ and A ₁₂ described above.

The definitions and preferred ranges of the alkylene group, cycloalkylene group and aromatic ring group represented by L ₁ ′ are the same as those in the alkylene group, cycloalkylene group and aromatic ring group as the divalent linking group represented by L _11. is there.

The definition and preferred range of the alkylene group and aromatic group in the group in which the alkylene group and the aromatic ring group represented by L ₁ ′ are combined are those in the alkylene group and aromatic ring group as the divalent linking group represented by L ₁₁ It is the same.

In one embodiment of the present invention, when A ₁₁ is an aromatic ring group, A ₁₂ and L ₁₁ are preferably a single bond.

In another embodiment of the present invention, when A ₁₂ is an aromatic ring group, L ₁₁ represents a divalent linking group. In the linking group L ₁₁ when A ₁₂ is an aromatic ring group, the atom directly bonded to A ₁₂ is not an oxygen atom. In this case, it is preferable atom bonded directly to A ₁₂ are carbon atoms. When A ₁₂ is an aromatic ring group, the linking group L ₁₁ is preferably an alkylene group or a cycloalkylene group, and more preferably a methylene group.

A ₁₃ represents a hydrogen atom or a substituent.
As the substituent represented by A _13, alkyl group, alkoxy group, alkoxycarbonyl group, an aryl group, hydroxy group, and the like. These groups excluding the hydroxy group may further have a substituent.

In one embodiment of the present invention, the substituent represented by A ₁₃ is preferably an alkyl group. The alkyl group represented by A ₁₃ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. And an alkyl group having 1 or 2 carbon atoms (that is, a methyl group or an ethyl group). Specific examples of the alkyl group for A ₁₃ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group. Can do.

A ₁₃ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, a methyl group or an ethyl group. It is more preferably a group, and particularly preferably a hydrogen atom.

In one embodiment, the group capable of leaving by the action of an acid represented by R ₁₁ (hereinafter also referred to as “acid leaving group”) is preferably a group represented by the following general formula (ALG1).

In general formula (ALG1),
R ₁ and R ₃ each independently represent a hydrogen atom or a substituent, and R ₂ represents a substituent. R ₁ and R ₂ may be bonded to each other to form a ring.

The substituent for R ₁ is preferably a group represented by * —C (R ₁₁₁ ) (R ₁₁₂ ) (R ₁₁₃ ). * Represents a bond connected to a carbon atom in the structure represented by the general formula (ALG1). R ₁₁₁ to R ₁₁₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group.

The alkyl group of R ₁₁₁ to R ₁₁₃ is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is more preferable. Specific examples of the alkyl group of R ₁₁₁ to R ₁₁₃ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, neopentyl group, hexyl group, 2 -Ethylhexyl group, octyl group, dodecyl group and the like can be mentioned, and the alkyl group of R ₁₁₁ to R ₁₁₃ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group or a t-butyl group.

At least two of R ₁₁₁ to R ₁₁₃ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, and all of R ₁₁₁ to R ₁₁₃ are an alkyl group, a cycloalkyl group, It preferably represents an aryl group, an aralkyl group or a heterocyclic group.

The cycloalkyl group of R ₁₁₁ to R ₁₁₃ may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 15 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. An alkyl group is more preferable, and a cycloalkyl group having 3 to 6 carbon atoms is still more preferable. Specific examples of the cycloalkyl group represented by R ₁₁₁ to R ₁₁₃ include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group, a cyclodecyl group, and a 1-adamantyl group. , 2-adamantyl group, 1-norbornyl group, 2-norbornyl group and the like. The cycloalkyl group of R ₁₁₁ to R ₁₁₃ is preferably a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group.

The aryl group of R ₁₁₁ to R ₁₁₃ is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and a plurality of aromatic rings are bonded to each other via a single bond. It also includes linked structures (eg, biphenyl group, terphenyl group). Specific examples of the aryl group of R ₁₁₁ to R ₁₁₃ include a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, a terphenyl group, and the like. The aryl group of R ₁₁₁ to R ₁₁₃ is preferably a phenyl group, a naphthyl group, or a biphenyl group.

The aralkyl group of R ₁₁₁ to R ₁₁₃ is preferably an aralkyl group having 6 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 12 carbon atoms. Specific examples of the aralkyl group of R ₁₁₁ to R ₁₁₃ include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and the like.

The heterocyclic group of R ₁₁₁ to R ₁₁₃ is preferably a heterocyclic group having 6 to 20 carbon atoms, and more preferably a heterocyclic group having 6 to 12 carbon atoms. Specific examples of the heterocyclic group represented by R ₁₁₁ to R ₁₁₃ include, for example, pyridyl group, pyrazyl group, tetrahydrofuranyl group, tetrahydropyranyl group, tetrahydrothiophene group, piperidyl group, piperazyl group, furanyl group, pyranyl group, chromanyl group. Etc.

The alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group as R ₁₁₁ to R ₁₁₃ may further have a substituent.

Examples of the substituent that the alkyl group as R ₁₁₁ to R ₁₁₃ may further have include a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, a halogen atom, and an alkoxy group. Group, aralkyloxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like. The above substituents may be bonded to each other to form a ring, and examples of the ring when the above substituents are bonded to each other to form a ring include a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group. .

Examples of the substituent that the cycloalkyl group as R ₁₁₁ to R ₁₁₃ can further have include the above-described groups as specific examples of the alkyl group and the substituent that the alkyl group can further have.

Note that the number of carbon atoms of the alkyl group and the number of carbon atoms of the substituent that the cycloalkyl group may further have are preferably 1 to 8, respectively.

Examples of the substituent that the aryl group, aralkyl group and heterocyclic group as R ₁₁₁ to R ₁₁₃ may further have include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, and an alkyl group. Group (preferably 1 to 15 carbon atoms), alkoxy group (preferably 1 to 15 carbon atoms), cycloalkyl group (preferably 3 to 15 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), alkoxycarbonyl Examples thereof include a group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), and the like.

At least two of R ₁₁₁ to R ₁₁₃ may form a ring with each other.
When at least two of R ₁₁₁ to R ₁₁₃ are bonded to each other to form a ring, examples of the ring formed include a tetrahydropyran ring, a cyclopentane ring, a cyclohexane ring, an adamantane ring, a norbornene ring, and a norbornane ring. . These rings may have a substituent, and examples of the substituent that can be included include an alkyl group and the groups described above as specific examples of the substituent that the alkyl group may further have.

When all of R ₁₁₁ to R ₁₁₃ are bonded to each other to form a ring, examples of the ring formed include an adamantane ring, norbornane ring, norbornene ring, bicyclo [2,2,2] octane ring, bicyclo [3, 1,1] heptane ring. Of these, an adamantane ring is particularly preferred. These may have a substituent, and examples of the substituent that may be included include the alkyl group and the groups described above as specific examples of the substituent that the alkyl group may further have.

The monovalent substituent of R ₂ is preferably a group represented by * -MQ. * Represents a bond linked to the oxygen atom of the general formula (ALG1). M represents a single bond or a divalent linking group. Q represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

The divalent linking group as M is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group), a cycloalkylene group. (Preferably a cycloalkylene group having 3 to 15 carbon atoms, such as a cyclopentylene group or a cyclohexylene group), —S—, —O—, —CO—, —CS—, —SO ₂ —, —N (R ₀ )-, or a combination of two or more thereof, and those having a total carbon number of 20 or less are preferred. Here, R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, Hexyl group and octyl group).

M is preferably a single bond, an alkylene group, or a divalent linking group comprising a combination of an alkylene group and at least one of —O—, —CO—, —CS— and —N (R ₀ ) —. A divalent linking group comprising a bond, an alkylene group, or a combination of an alkylene group and —O— is more preferable. Here, R ₀ has the same meaning as R ₀ described above.

M may further have a substituent, and the substituent that M may further have is the same as the substituent that the alkyl group of R ₁₁₁ to R ₁₁₃ described above may have.

Specific examples and preferred examples of the alkyl group as Q are the same as those described for the alkyl group as R ₁₁₁ to R ₁₁₃ described above, for example.

The cycloalkyl group as Q may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, a 2-norbornyl group, Bornyl group, isobornyl group, 4-tetracyclo [6.2.1.1 ^3,6 . A 0 ^2,7 ] dodecyl group, an 8-tricyclo [5.2.1.0 ^2,6 ] decyl group, and a 2-bicyclo [2.2.1] heptyl group. Of these, a cyclopentyl group, a cyclohexyl group, a 2-adamantyl group, an 8-tricyclo [5.2.1.0 ^2,6 ] decyl group, and a 2-bicyclo [2.2.1] heptyl group are preferable.

Specific examples and preferred examples of the aryl group as Q are the same as those described for the aryl group as R ₁₁₁ to R ₁₁₃ described above, for example.

Specific examples and preferred examples of the heterocyclic group as Q are the same as those described for the heterocyclic group as R ₁₁₁ to R ₁₁₃ described above, for example.

The alkyl group, cycloalkyl group, aryl group and heterocyclic group as Q may have a substituent, for example, an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group. And an alkoxycarbonyl group.

R ₂ is preferably an alkyl group, an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, an aralkyl group, an aryloxyalkyl group or a heterocyclic group, and more preferably an alkyl group or a cycloalkyl group. . Alkyl group, a cycloalkyl group of the "cycloalkyl group" and "alkyl group substituted with a cycloalkyl group" as R ₂ as R _2, and "aralkyl group as the group represented by R ₂ (arylalkyl Specific examples and preferred examples of the aryl group in the “group)” and “aryloxyalkyl group” are the same as those described for the alkyl group, cycloalkyl group and aryl group as Q, respectively.

Specific examples and preferred examples of the alkyl moiety in the “alkyl group substituted by a cycloalkyl group”, “aralkyl group (arylalkyl group)” and “aryloxyalkyl group” as R ₂ are the alkylene group as M, respectively. This is the same as that described in.

Specific examples and preferred examples of the heterocyclic group as R ₂ are the same as those described for the heterocyclic group as Q.

Specific examples of the substituent represented by R ₂ include a methyl group, an ethyl group, an isopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylethyl group, a 2-adamantyl group, and 8-tricyclo [5.2.1. 0 ^2,6 ] decyl group, 2-bicyclo [2.2.1] heptyl group, benzyl group, 2-phenethyl group, 2-phenoxyethylene group and the like.

R ₁ and R ₂ may be bonded to each other to form a ring, and the ring formed by bonding R ₁ and R ₂ to each other is preferably an oxygen-containing heterocyclic ring. The oxygen-containing heterocyclic structure may be monocyclic, polycyclic or spirocyclic, and is preferably a monocyclic oxygen-containing heterocyclic structure, preferably having 3 to 10 carbon atoms, more preferably Is 4 or 5.

In one embodiment of the present invention, when A ₁₂ is an aromatic ring and L ₁₁ is a divalent linking group, it is preferable that R ₁ and R ₂ are not bonded to each other to form a ring.

As described above, when M is a divalent linking group, Q may be bonded to M via a single bond or another linking group to form a ring. Examples of the other linking group include an alkylene group (preferably an alkylene group having 1 to 3 carbon atoms), and the ring formed is preferably a 5- or 6-membered ring.

Examples of the substituent for R ₃ include an alkyl group and a cycloalkyl group. R ₃ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, a methyl group or ethyl group. It is more preferably a group, and particularly preferably a hydrogen atom.

In another form, the acid leaving group represented by R ₁₁ is preferably a group represented by the following general formula (ALG2).

In general formula (ALG2),
R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group. Two selected from R ₄ , R ₅ and R ₆ may be bonded to each other to form a ring.
The alkyl group for R ₄ to R ₆ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.

Examples of the cycloalkyl group represented by R ₄ to R ₆ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Groups are preferred.

Examples of the ring formed by combining two of R ₄ to R ₆ include a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, etc. The polycyclic cycloalkyl group is preferable. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.

In the ring formed by combining two of R ₄ to R ₆ , for example, one of the methylene groups constituting the ring is replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. May be.

Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, an alkoxy group. Examples thereof include carbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.

In one embodiment of the present invention, the leaving group represented by General Formula (ALG2) is, for example, R ₄ is a methyl group or an ethyl group, and R ₅ and R ₆ are bonded to form the above cycloalkyl group. The aspect which forms is preferable.

In one embodiment of the present invention, when the acid leaving group represented by R ₃₁ is a group represented by the general formula (ALG2), from R ₄ , R _5, and R _{6 in} the general formula (ALG2) The two selected are preferably bonded to each other to form a ring.

Examples of the acid leaving group R ₁₁ other than the groups represented by the general formulas (ALG1) and (ALG2) described above include, for example, —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), —C (═O ) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₀₁ ) (R ₀₂ ) —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) Etc.

In the formula, R ₃₆ to R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. R ₀₁ to R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

In the general formula (Ab1), r ₁₁ is an integer of 1 or more, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.

In one embodiment, the repeating unit (Aba) is preferably a repeating unit represented by the general formula (Ab2).

In the general formula (Ab2), the acid leaving group represented by R ₂₁ has the same meaning as the acid leaving group represented by R ₁₁ in the general formula (Ab1) described above, and the general formula (ALG1) or A group represented by the general formula (ALG2) is preferable.

R ₂₂ represents a substituent that the aromatic ring in the formula may have, and examples thereof include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, and a hydroxy group.

q ₂₁ represents the number of substitutions by R ₂₂ , is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

The divalent linking group represented by L ₂₁ has the same meaning as the divalent linking group represented by L11 in the general formula (Ab1) described above. In one embodiment of the present invention, L ₂₁ is preferably a single bond.

p ₂₁ is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In another embodiment, the repeating unit (Aba) is preferably a repeating unit represented by the general formula (Ab3).

Where
R ₃₁ represents a group capable of leaving by the action of an acid, R ₃₂ represents a substituent, L ₃₁ represents a divalent linking group, p ₃₁ represents 0 or an integer of 1 or more, and A ₃₁ ₃₁ represents a hydrogen atom or a substituent, A ₃₃ represents a hydrogen atom or a substituent, q ₃₁ represents 0 or an integer of 1 or more, and r ₃₁ represents an integer of 1 or more.

In the general formula (Ab3), the acid leaving group represented by R ₃₁ has the same meaning as the acid leaving group represented by R ₁₁ in the general formula (Ab1) described above, and the general formula (ALG1) or A group represented by the general formula (ALG2) is preferable.

In one embodiment of the present invention, when the acid leaving group represented by R ₃₁ is a group represented by the general formula (ALG1), R ₁ and R ₂ in the general formula (ALG1) are bonded to each other. It is preferable not to form a ring.

R ₃₂ represents a substituent that the aromatic ring in the formula may have, and examples thereof include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, and a hydroxy group.

q ₃₁ represents the number of substitutions by R ₃₂ , and is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

The divalent linking group represented by L ₃₁ has the same meaning as the divalent linking group represented by L ₁₁ in the general formula (Ab1) described above. In one embodiment of the present invention, L ₃₁ is preferably an alkylene group or a cycloalkylene group, and more preferably a methylene group.

A ₃₁ has the same meaning as _{A 11} in general formula _{(Ab1), A 33} is as defined to _{A 13} in the general formula (Ab1).

p ₃₁ is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. r ₃₁ is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Specific examples of the repeating unit (Aba) are shown below, but the present invention is not limited to this.

The content of the repeating units represented by the above general formula (Ab1) in the resin (Ab) (the total when there are a plurality of types) is 10 to 90 mol% with respect to all the repeating units in the resin (Ab). It is preferably 20 to 75 mol%, more preferably 30 to 60 mol%.

Resin (Ab) may further have an acid-decomposable group that decomposes by the action of an acid to generate a polar group, separately from the repeating unit (Aba).

Examples of the polar group include a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a sulfonic acid group, and a thiol group.

Examples of the group capable of leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), —C (═O) — OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), —C (R ₀₁ ) (R ₀₂ ) —C (═O) —O— C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) and the like can be mentioned.

In one embodiment of the present invention, the resin (Ab) preferably has a repeating unit represented by the following general formula (A).

In general formula (A),
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. (However, R ₄₂ may be bonded to Ar ₄ or X ₄ to form a ring, and R ₄₂ in this case represents a single bond or an alkylene group.)

X ₄ represents a single bond, an alkylene group, —COO—, or —CONR ₆₄ —. (Here, R ₆₄ represents a hydrogen atom or an alkyl group.)

L ₄ represents a single bond, —COO—, or an alkylene group.

Ar ₄ represents an (n + 1) -valent aromatic ring group, and when bonded to R ₄₂ to form a ring, represents an (n + 2) -valent aromatic ring group.

N represents an integer of 1 to 4.

The alkyl group for R ₄₁ , R ₄₂ and R ₄₃ is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, which may have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, particularly preferably alkyl groups having 3 or less carbon atoms.

Specific examples and preferred examples of the alkyl group contained in the alkoxycarbonyl group of R _41, _R _{42, R 43} are the same as those in the above-described alkyl group _R _41, R _{42, R 43.}

Examples of the halogen atom for R ₄₁ , R ₄₂ and R ₄₃ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferred.

Ar ₄ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or the like. Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.

Specific examples of the (n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.

The (n + 1) -valent aromatic ring group may further have a substituent.

The alkylene group for L ₄ is preferably an alkylene group having 1 to 8 carbon atoms such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group.

The alkylene group represented by X ₄ is the same as that in the alkylene group as the divalent linking group represented by L in formula (Ab), and the preferred range is also the same.

When R ₄₂ and Ar ₄ or X ₄ are combined to form a ring, the alkylene group as R ₄₂ may be linear or branched and has 1 to 5 carbon atoms. preferable.

When R ₄₂ and X ₄ are combined to form a ring, the alkylene group as X ₄ may be linear or branched, and preferably has 1 to 5 carbon atoms.

_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64} _in, the same as the alkyl group of _R 41 _~ R _43.

X ₄ is preferably a single bond, an alkylene group, —COO— or —CONH—, and more preferably a single bond or —COO—.

Ar ₄ is more preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group.

The repeating unit (b) preferably has a hydroxystyrene structure. That is, Ar ₄ is preferably a benzene ring group.

Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups and the like, and the substituent preferably has 8 or less carbon atoms.

The repeating unit represented by the general formula (A) is preferably a repeating unit represented by the following formula (A1) or (A2). R ″ represents a hydrogen atom or a methyl group.

As specific examples of the repeating unit (b) represented by the general formula (A), in addition to those shown below, those described in paragraphs 0226 to 0227 of JP 2014-41328 A can be used, These contents are incorporated herein.

Resin (Ab) may contain two or more types of repeating units represented by the general formula (A).

The content of the repeating unit represented by the above general formula (A) in the resin (Ab) (the total in the case of containing a plurality of types) is relative to the developer containing an organic solvent in the actinic ray-sensitive or radiation-sensitive film. From the viewpoint of improving the dissolution contrast, it is preferably 10 to 70 mol%, more preferably 15 to 55 mol%, most preferably 20 to 40 mol%, based on all repeating units in the resin (Ab). is there.

Resin (Ab) may further contain a repeating unit represented by the following general formula (A5).

In formula (A5),
X is a hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, aryl group, carboxyl group, alkyloxycarbonyl group, alkylcarbonyloxy group, or Represents an aralkyl group.

A ₄ represents a hydrocarbon group that is not eliminated by the action of an acid.

In the general formula (A5), examples of the hydrocarbon group that is not eliminated by the action of the acid A ₄ include hydrocarbon groups other than the acid-decomposable groups, such as an alkyl that is not eliminated by the action of the acid. A group (preferably having 1 to 15 carbon atoms), a cycloalkyl group that is not eliminated by the action of an acid (preferably 3 to 15 carbon atoms), an aryl group that is not eliminated by the action of an acid (preferably having 6 to 15 carbon atoms) Can be mentioned.

The hydrocarbon group that is not eliminated by the action of the acid of A ₄ may be further substituted with a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or the like.

Hereinafter, specific examples of the repeating unit represented by the general formula (A5) will be given, but the invention is not limited thereto.

In addition, as an aspect of the repeating unit having an acid-decomposable group different from the repeating unit exemplified above, the resin (Ab) may have a repeating unit that generates an alcoholic hydroxyl group. In this case, the repeating unit that generates an alcoholic hydroxyl group is preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-10). The repeating unit that generates an alcoholic hydroxyl group is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-3). More preferably, it is represented by:

Where
Each Ra independently represents a hydrogen atom, an alkyl group or a group represented by —CH ₂ —O—Ra ₂ . Here, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group.

R ₁ represents an (n + 1) valent organic group.

R ₂ independently represents a single bond or an (n + 1) -valent organic group when m ≧ 2.

OP each independently represents the above group which decomposes by the action of an acid to produce an alcoholic hydroxy group. When n ≧ 2 and / or m ≧ 2, two or more OPs may be bonded to each other to form a ring.

W represents a methylene group, an oxygen atom or a sulfur atom.

n and m represent an integer of 1 or more. In the general formula (I-2), (I-3) or (I-8), n is 1 when R ₂ represents a single bond.

L represents an integer of 0 or more.

L ₁ represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ — or —SO ₂ NH—. Here, Ar represents a divalent aromatic ring group.

R each independently represents a hydrogen atom or an alkyl group.

R ₀ represents a hydrogen atom or an organic group.

L ₃ represents a (m + 2) -valent linking group.

R ^L each independently represents an (n + 1) -valent linking group when m ≧ 2.

R ^S each independently represents a substituent when p ≧ 2. For p ≧ 2, plural structured R ^S may be bonded to each other to form a ring.

P represents an integer from 0 to 3.

Ra represents a hydrogen atom, an alkyl group, or a group represented by —CH ₂ —O—Ra ₂ . Ra is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group.

W represents a methylene group, an oxygen atom or a sulfur atom. W is preferably a methylene group or an oxygen atom.

R ₁ represents an (n + 1) valent organic group. R ₁ is preferably a non-aromatic hydrocarbon group. In this case, R ₁ may be a chain hydrocarbon group or an alicyclic hydrocarbon group. R ₁ is more preferably an alicyclic hydrocarbon group.

R ₂ represents a single bond or an (n + 1) valent organic group. R ₂ is preferably a single bond or a non-aromatic hydrocarbon group. In this case, R ₂ may be a chain hydrocarbon group or an alicyclic hydrocarbon group.

When R ₁ and / or R ₂ is a chain hydrocarbon group, the chain hydrocarbon group may be linear or branched. In addition, the chain hydrocarbon group preferably has 1 to 8 carbon atoms. For example, when R ₁ and / or R ₂ is an alkylene group, R ₁ and / or R ₂ is a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group or sec- A butylene group is preferred.

When R ₁ and / or R ₂ is an alicyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. This alicyclic hydrocarbon group has, for example, a monocyclo, bicyclo, tricyclo or tetracyclo structure. The carbon number of the alicyclic hydrocarbon group is usually 5 or more, preferably 6 to 30, and more preferably 7 to 25.

Examples of the alicyclic hydrocarbon group include those having the partial structures listed below. Each of these partial structures may have a substituent. In each of these partial structures, the methylene group (—CH ₂ —) includes an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group [—C (═O) —], a sulfonyl group [— —S (═O) ₂ —], sulfinyl group [—S (═O) —], or imino group [—N (R) —] (where R is a hydrogen atom or an alkyl group) may be substituted.

For example, when R ₁ and / or R ₂ is a cycloalkylene group, R ₁ and / or R ₂ may be an adamantylene group, a noradamantylene group, a decahydronaphthylene group, a tricyclodecanylene group, a tetracyclododeca group. Nylene group, norbornylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclodecanylene group, or cyclododecanylene group are preferable, and adamantylene group, norbornylene group, cyclohexylene group, cyclopentylene It is more preferable that they are a len group, a tetracyclododecanylene group, or a tricyclodecanylene group.

The non-aromatic hydrocarbon group of R ₁ and / or R ₂ may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms. The above alkyl group, alkoxy group and alkoxycarbonyl group may further have a substituent. As this substituent, a hydroxy group, a halogen atom, and an alkoxy group are mentioned, for example.

L ₁ represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ — or —SO ₂ NH—. Here, Ar represents a divalent aromatic ring group. L ₁ is preferably a linking group represented by —COO—, —CONH— or —Ar—, and more preferably a linking group represented by —COO— or —CONH—.

R represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. R is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

R ₀ represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an alkynyl group, and an alkenyl group. R ₀ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.

L ₃ represents a (m + 2) -valent linking group. That is, L ₃ represents a trivalent or higher linking group. Examples of such a linking group include corresponding groups in specific examples described later.

R ^L represents a (n + 1) -valent linking group. That is, R ^L represents a divalent or higher linking group. Examples of such a linking group include an alkylene group, a cycloalkylene group, and corresponding groups in the specific examples described below. R ^L may be bonded to each other or bonded to the following R ^S to form a ring structure.

R ^S represents a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, and a halogen atom.

N is an integer of 1 or more. n is preferably an integer of 1 to 3, and more preferably 1 or 2. When n is 2 or more, it is possible to further improve the dissolution contrast with respect to a developer containing an organic solvent. Accordingly, in this way, the limit resolution and roughness characteristics can be further improved.

M is an integer of 1 or more. m is preferably an integer of 1 to 3, and more preferably 1 or 2.

L is an integer of 0 or more. l is preferably 0 or 1.

P is an integer from 0 to 3.

The repeating unit that generates an alcoholic hydroxyl group is preferably a repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group.

Specific examples of the repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group are shown below. In specific examples, Ra and OP have the same meanings as in general formulas (I-1) to (I-3). In addition, when a plurality of OPs are bonded to each other to form a ring, the corresponding ring structure is represented as “OPO” for convenience.

The group that decomposes by the action of an acid to produce an alcoholic hydroxy group is preferably represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-4).

Where
R ₃ each independently represents a hydrogen atom or a monovalent organic group. R ₃ may be bonded to each other to form a ring.

R ₄ each independently represents a monovalent organic group. R ₄ may be bonded to each other to form a ring. R ₃ and R ₄ may be bonded to each other to form a ring.

R ₅ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. At least two R ₅ may be bonded to each other to form a ring. However, when one or two of the three R ₅ are hydrogen atoms, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group.

The group capable of decomposing by the action of an acid to produce an alcoholic hydroxy group is also preferably represented by at least one selected from the group consisting of the following general formulas (II-5) to (II-9).

Where
R ₄ has the same meaning as in formulas (II-1) to (II-3).

R ₆ each independently represents a hydrogen atom or a monovalent organic group. R ₆ may be bonded to each other to form a ring.

The group that decomposes by the action of an acid to produce an alcoholic hydroxy group is more preferably represented by at least one selected from the general formulas (II-1) to (II-3). More preferably, it is represented by 1) or (II-3), and particularly preferably represented by formula (II-1).

R ₃ represents a hydrogen atom or a monovalent organic group as described above. R ₃ is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group.

The alkyl group for R ₃ may be linear or branched. The number of carbon atoms of the alkyl group represented by R ₃ is preferably 1 to 10, and more preferably 1 to 3. Examples of the alkyl group for R ₃ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

The cycloalkyl group for R ₃ may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkyl group represented by R ₃ is preferably 3 to 10, and more preferably 4 to 8. Examples of the cycloalkyl group represented by R ₃ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

In general formula (II-1), at least one of R ₃ is preferably a monovalent organic group. When such a configuration is employed, particularly high sensitivity can be achieved.

R ₄ represents a monovalent organic group. R ₄ is preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group. These alkyl groups and cycloalkyl groups may have a substituent.

The alkyl group represented by R ₄ preferably has no substituent, or preferably has one or more aryl groups and / or one or more silyl groups as substituents. The carbon number of the unsubstituted alkyl group is preferably 1-20. The alkyl group moiety in the alkyl group substituted with one or more aryl groups preferably has 1 to 25 carbon atoms. The number of carbon atoms of the alkyl group moiety in the alkyl group substituted with one or more silyl groups is preferably 1-30. Further, when the cycloalkyl group of R ₄ has no substituent, the carbon number thereof is preferably 3-20.

R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. However, when one or two of the three R ₅ are hydrogen atoms, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group. R ₅ is preferably a hydrogen atom or an alkyl group. The alkyl group may have a substituent or may not have a substituent. When the alkyl group does not have a substituent, the carbon number thereof is preferably 1 to 6, and preferably 1 to 3.

R ₆ represents a hydrogen atom or a monovalent organic group as described above. R ₆ is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or an alkyl group having no substituent. R ₆ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and having no substituent.

Examples of the alkyl group and cycloalkyl group of R ₄ , R _5, and R ₆ include the same as those described above for R ₃ .

Specific examples of groups that decompose by the action of an acid to produce an alcoholic hydroxy group are shown below.

Specific examples of the repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group are shown below. In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

The above repeating unit having an acid-decomposable group may be one type or a combination of two or more types.

The content of the repeating unit having an acid-decomposable group in the resin (Ab) (when there are a plurality of types) is preferably 10 to 90 mol% with respect to all the repeating units in the resin (Ab), More preferably, it is 30 to 80 mol%, and most preferably 50 to 70 mol%.

Resin (Ab) may further contain a repeating unit represented by the following general formula (4).

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. S represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

Specific examples of the repeating unit represented by the general formula (4) include, for example, those described in paragraphs 0195 to 0209 of JP2014-41328A, paragraphs 0016 to 0145 of JP2013-54196A, and the like. The contents of which are incorporated herein by reference.

The content of the repeating unit represented by the general formula (4) in the resin (Ab) is preferably in the range of 1 to 40 mol% with respect to all the repeating units of the resin (Ab), and in the range of 2 to 30 mol%. Is more preferable, and the range of 5 to 25 mol% is particularly preferable.

The resin (Ab) preferably contains a repeating unit (b ′) having a polar group, which is different from the repeating unit represented by the general formula (A). By including the repeating unit (b ′), for example, the sensitivity of the composition containing a resin can be improved. The repeating unit (b ′) is preferably a non-acid-decomposable repeating unit (that is, having no acid-decomposable group).

Examples of the “polar group” that can be contained in the repeating unit (b ′) include the following (1) to (4). In the following, “electronegativity” means a value by Pauling.

(1) A functional group including a structure in which an oxygen atom and an atom having an electronegativity difference of 1.1 or more are bonded by a single bond. Examples of such a polar group include a hydroxy group and the like. And a group containing a structure represented by O—H.

(2) Functional group including a structure in which a nitrogen atom and an atom having a difference in electronegativity of the nitrogen atom of 0.6 or more are bonded by a single bond. Examples of such a polar group include an amino group and the like. And a group containing a structure represented by NH.

(3) Functional group including a structure in which two atoms having electronegativity different by 0.5 or more are bonded by a double bond or a triple bond. Examples of such a polar group include C≡N, C═O, N = And a group containing a structure represented by O, S═O or C═N.

(4) Functional group having an ionic moiety Examples of such a polar group include a group having a moiety represented by N ⁺ or S ⁺ .
Specific examples of the partial structure that can be included in the “polar group” are given below.

The polar group that can be contained in the repeating unit (b ′) is a hydroxyl group, a cyano group, a lactone group, a sultone group, a carboxylic acid group, a sulfonic acid group, an amide group, a sulfonamide group, an ammonium group, a sulfonium group, a carbonate group (— O—CO—O—) (for example, cyclic carbonate structure, etc.) and a group formed by combining two or more of these are preferable, and an alcoholic hydroxy group, cyano group, lactone group, sultone group, or A group containing a cyanolactone structure is particularly preferred.

When the resin further contains a repeating unit having an alcoholic hydroxy group, the exposure latitude (EL) of the composition containing the resin can be further improved.

If the resin further contains a repeating unit having a cyano group, the sensitivity of the resin-containing composition can be further improved.

If the resin further contains a repeating unit having a lactone group, the dissolution contrast with respect to a developer containing an organic solvent can be further improved. This also makes it possible to further improve the dry etching resistance, coating properties, and adhesion to the substrate of the resin-containing composition.

When the resin further contains a repeating unit having a group containing a lactone structure having a cyano group, the dissolution contrast with respect to the developer containing an organic solvent can be further improved. This also makes it possible to further improve the sensitivity, dry etching resistance, applicability, and adhesion to the substrate of the composition containing the resin. In addition, this makes it possible for a single repeating unit to have a function attributable to each of the cyano group and the lactone group, thereby further increasing the degree of freedom in designing the resin.

When the polar group of the repeating unit (b ′) is an alcoholic hydroxy group, it is preferably represented by at least one selected from the group consisting of the following general formulas (I-1H) to (I-10H) . In particular, it is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1H) to (I-3H), and is preferably represented by the following general formula (I-1H). Further preferred.

In the formula, Ra, R ₁ , R ₂ , W, n, m, l, L ₁ , R, R ₀ , L ₃ , R ^L , R ^S and p are represented by the general formulas (I-1) to (I− It is synonymous with each of 10).

A repeating unit having a group capable of decomposing by the action of an acid to generate an alcoholic hydroxy group, and a repeating unit represented by at least one selected from the group consisting of the above general formulas (I-1H) to (I-10H) When the unit is used in combination, for example, by suppressing acid diffusion due to an alcoholic hydroxy group and increasing sensitivity due to a group that decomposes by the action of an acid to generate an alcoholic hydroxy group, without degrading other performances, The exposure latitude (EL) can be improved.

In the case of having an alcoholic hydroxy group, the content of the repeating unit is preferably 1 to 60 mol%, more preferably 3 to 50 mol%, still more preferably 5 to 40 mol%, based on all repeating units in the resin (Ab). It is.

Specific examples of the repeating unit represented by any one of the general formulas (I-1H) to (I-10H) are shown below. In specific examples, Ra has the same meaning as that in formulas (I-1H) to (I-10H).

When the polar group of the repeating unit (b ′) is an alcoholic hydroxy group or a cyano group, one embodiment of a preferable repeating unit is a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. Can be mentioned. At this time, it is preferable not to have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIIc) are preferred. This improves the substrate adhesion and developer compatibility.

In the general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. In the general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms.

Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIIc) include the repeating units represented by the following general formulas (AIIa) to (AIIc).

In the general formulas (AIIa) to (AIIc),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

_R ₂ c ~ R ₄ c is in the general formula (VIIa) ~ _(VIIc), the same meanings as _R 2 c ~ R ₄ c.

The resin (Ab) may or may not contain a repeating unit having a hydroxyl group or a cyano group, but when it is contained, the content of the repeating unit having a hydroxyl group or a cyano group in the resin (Ab) The amount is preferably 1 to 60 mol%, more preferably 3 to 50 mol%, still more preferably 5 to 40 mol%, based on all repeating units.

Specific examples of the repeating unit having a hydroxyl group or a cyano group are listed below, but the present invention is not limited thereto.

The repeating unit (b ′) may be a repeating unit having a lactone structure as a polar group.

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

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).

Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group obtained by combining these. Ab is preferably a single bond or a divalent linking group represented by —Ab ₁ —CO ₂ —.

Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

V represents a group having a lactone structure.

As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in the form to be formed are preferred. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), (LC1-14).

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

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

The resin (Ab) may or may not contain a repeating unit having a lactone structure, but when it contains a repeating unit having a lactone structure, the content of the repeating unit having a lactone structure in the resin (Ab) Is preferably in the range of 1 to 70 mol%, more preferably in the range of 3 to 65 mol%, and still more preferably in the range of 5 to 60 mol% with respect to all repeating units.

Specific examples of the repeating unit having a lactone structure in the resin (Ab) are shown below, but the present invention is not limited thereto. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The sultone groups possessed by the resin (Ab) are preferably the following general formulas (SL-1) and (SL-2). In the formula, Rb ₂ and n ₂ have the same meanings as in the general formulas (LC1-1) to (LC1-17) described above.

As the repeating unit containing a sultone group that the resin (Ab) has, a lactone group in the repeating unit having a lactone group described above is preferably substituted with a sultone group.

In addition, it is also a particularly preferable aspect that the polar group that the repeating unit (b ′) may have is an acidic group. Preferred acidic groups include phenolic hydroxyl groups, carboxylic acid groups, sulfonic acid groups, fluorinated alcohol groups (eg hexafluoroisopropanol group), sulfonamide groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, Alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, A tris (alkylsulfonyl) methylene group is mentioned. Of these, the repeating unit (b) is more preferably a repeating unit having a carboxyl group. By containing the repeating unit having an acidic group, the resolution in the contact hole application is increased. The repeating unit having an acidic group includes a repeating unit in which an acidic group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acidic group in the main chain of the resin through a linking group. It is preferable to use a polymerization initiator or a chain transfer agent having a repeating unit bonded to each other, or an acidic group, at the time of polymerization and introduce it at the end of the polymer chain. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

The acidic group that the repeating unit (b ′) may have may or may not contain an aromatic ring. When the repeating unit (b ′) has an acidic group, the content of the repeating unit having an acidic group is preferably 30 mol% or less, and 20 mol% or less with respect to all the repeating units in the resin (Ab). It is more preferable that When resin (Ab) contains the repeating unit which has an acidic group, content of the repeating unit which has an acidic group in resin (Ab) is 1 mol% or more normally.

Specific examples of the repeating unit having an acidic group are shown below, but the present invention is not limited thereto.

In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

Resin (Ab) may have a repeating unit (c) having a plurality of aromatic rings represented by the following general formula (c1).

In general formula (c1),
R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or a nitro group;
Y represents a single bond or a divalent linking group;
Z represents a single bond or a divalent linking group;
Ar represents an aromatic ring group;
p represents an integer of 1 or more.

Regarding the repeating unit represented by the general formula (c1), the contents described in paragraphs 0265 to 0279 of JP 2014-41328 A can be used, and these contents are incorporated in the present specification.

The resin (Ab) may or may not contain the repeating unit (c), but when it is contained, the content of the repeating unit (c) is 1 to 30 with respect to the entire repeating unit of the resin (Ab). It is preferably in the range of mol%, more preferably in the range of 1 to 20 mol%, still more preferably in the range of 1 to 15 mol%. The repeating unit (c) contained in the resin (Ab) may contain a combination of two or more types.

The resin (Ab) in the present invention may appropriately have a repeating unit other than the repeating units (a) to (c). As an example of such a repeating unit, it can further have a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, the above-mentioned acid group, hydroxyl group, and cyano group) and does not exhibit acid decomposability. . Thereby, the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

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

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

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

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

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5.2.1.0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group described above may further have a substituent, and examples of the substituent that may further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. The group can be mentioned.

Examples of the hydrogen atom substituent include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferable acyl groups include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The resin (Ab) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. The content is preferably from 1 to 20 mol%, more preferably from 5 to 15 mol%, based on all repeating units in the resin (Ab).

Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

In addition, the resin (Ab) may contain the following monomer components in view of effects such as improvement in Tg, improvement in dry edging resistance, and the above-described internal filter for out-of-band light.

Resin (Ab) may contain a repeating unit represented by the following general formula (V) or the following general formula (VI).

Where
R ₆ and R ₇ are each independently a hydrogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, It represents a halogen atom, an ester group (—OCOR or —COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.

n ₃ represents an integer of 0 to 6.

X ⁴ is a methylene group, an oxygen atom or a sulfur atom.

Specific examples of the repeating unit represented by the general formula (V) or the general formula (VI) are shown below, but are not limited thereto.

Moreover, the resin (Ab) may have a repeating unit having a cyclic carbonate structure.

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

In general formula (A-1), R _A ¹ represents a hydrogen atom or an alkyl group.

R _A ² each independently represents a substituent when n is 2 or more.

A represents a single bond or a divalent linking group.

Z represents an atomic group forming a monocyclic or polycyclic structure together with a group represented by —O—C (═O) —O— in the formula.

N represents an integer of 0 or more.

Regarding the repeating unit represented by the general formula (A-1), the contents described in paragraphs 0293 to 0304 of JP-A-2014-41328 can be used, and these contents are incorporated in the present specification.

In the resin (Ab) used in the composition of the present invention, the content molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist requirements. It is appropriately set in order to adjust the resolution, heat resistance, sensitivity, etc., which are performance.

Specific examples of the resin (Ab) are given below, but the present invention is not limited thereto.

The form of the resin (Ab) of the present invention may be any of random type, block type, comb type, and star type.

Resin (Ab) can be synthesized, for example, by radical, cation, or anionic polymerization of unsaturated monomers corresponding to each structure. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.

For example, as a general synthesis method, an unsaturated monomer and a polymerization initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the unsaturated monomer and the polymerization initiator is added to the heating solvent for 1 to 10 hours. The dropping polymerization method etc. which are dropped and added over are mentioned, and the dropping polymerization method is preferable.

Examples of the solvent used for the polymerization include a solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition described below, and more preferably the composition of the present invention. Polymerization is preferably carried out using the same solvent as used in the above. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If necessary, the polymerization may be performed in the presence of a chain transfer agent (for example, alkyl mercaptan).

The concentration of the reaction is 5 to 70% by mass, preferably 10 to 50% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 40 ° C to 100 ° C.
The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, and more preferably 1 to 12 hours.

After the reaction is complete, cool to room temperature and purify. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.

The solvent used for the precipitation or reprecipitation operation from the polymer solution (precipitation or reprecipitation solvent) may be any poor solvent for this polymer. Depending on the type of polymer, hydrocarbon, halogenated hydrocarbon, nitro A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally, 100 to 10,000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300 to 1000 parts by mass.

The temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

Precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

It should be noted that once the resin is precipitated and separated, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again in the solvent. (Step c), and then, the resin solution A is brought into contact with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.

The molecular weight of the resin (Ab) according to the present invention is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 60000, and in the range of 2000 to 30000. It is particularly preferred. By setting the weight average molecular weight in the range of 1,000 to 100,000, it is possible to prevent deterioration of heat resistance and dry etching resistance, and also prevent deterioration of developability and film formation due to increased viscosity. be able to. Here, the weight average molecular weight of the resin indicates a polystyrene equivalent molecular weight measured by GPC (Gel Permeation Chromatography) (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

Resin (Ab) of this invention can be used individually by 1 type or in combination of 2 or more types. The content of the resin (Ab) is preferably 20 to 99% by mass, more preferably 30 to 89% by mass, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. 40 to 79% by mass is particularly preferable.
[2] Resin (B) which is different from resin (Ab) and decomposes by the action of an acid and changes its solubility in a developer.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is different from the resin (Ab) in that it decomposes by the action of an acid and changes its solubility in a developer (hereinafter also referred to as a resin (B)). You may contain.

Resin (B) is a resin having a structure in which a polar group is protected by a leaving group that decomposes and leaves under the action of an acid (hereinafter also referred to as “acid-decomposable group”).

Resin (B) preferably has a repeating unit having an acid-decomposable group.

Resin (B) can be synthesized according to a conventional method (for example, radical polymerization).

The weight average molecular weight of the resin (B) is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000, and even more preferably from 3,000 to 15 in terms of polystyrene by GPC method. 1,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

The degree of dispersion (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 1.7. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

Resin (B) may be used in combination of two or more.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain the resin (B). However, when it is contained, the amount of the resin (B) added is the actinic ray-sensitive or sensitive. It is usually 1 to 50% by mass, preferably 1 to 30% by mass, and particularly preferably 1 to 15% by mass with respect to the total solid content of the radiation resin composition.

The resin (B) is described in paragraphs [0059] to [0169] of JP-A No. 2010-217884, and described in paragraphs [0214] to [0594] of Japanese Patent Application No. 2011-217048. Things.
[3] (B) Compound that generates acid upon irradiation with actinic ray or radiation The composition of the present invention comprises a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generator” or “photoacid generation”). It is preferable to contain an agent.

The acid generator is not particularly limited as long as it is a publicly known acid generator, but upon irradiation with actinic rays or radiation, at least any of organic acids such as sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide. Compounds that generate such are preferred.

The compound (B) that generates an acid upon irradiation with actinic rays or radiation may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.

When the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and 1000 or less. Is more preferable.

When the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the acid-decomposable resin described above. It may be incorporated in a resin different from the resin.

More preferably, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be mentioned.

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.

The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

Two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two _{members out} of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

The aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. Examples include 3 to 30 cycloalkyl groups.

The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably a carbon atom) Number 6 to 20), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . Regarding the aryl group and ring structure of each group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like.

Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

In addition, the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.

Examples of other non-nucleophilic anions include fluorinated phosphorus (eg, PF ₆ ⁻ ), fluorinated boron (eg, BF ₄ ⁻ ), fluorinated antimony (eg, SbF ₆ ⁻ ), and the like. .

Examples of the non-nucleophilic anion include an aliphatic sulfonate anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.

From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

Also, as the non-nucleophilic anion, an anion represented by the following general formula (AN1) can be mentioned as a preferred embodiment.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R ¹ and R ² , they may be the same or different.

L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.

A represents a cyclic organic group.

X represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.

The alkyl group in the alkyl group substituted with a fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ may be mentioned, among which a fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent for R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _15. _{_{_{_{, C 8 F 17, CH 2}}}} CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which CF ₃ is preferable.

R ¹ and R ² are preferably a fluorine atom or CF ₃ .

X is preferably 1 to 10, and more preferably 1 to 5.

Y is preferably 0 to 4, more preferably 0.

Z is preferably from 0 to 5, and more preferably from 0 to 3.

The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred. Of these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).

The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group. A polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.

Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.

Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.

In addition, examples of the cyclic organic group may include a lactone structure, and specific examples include those represented by the general formulas (LC1-1) to (LC1-17) that may be included in the resin (Ab). Can be mentioned.

The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spiro ring, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide Group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

_Examples of the organic group for R ₂₀₁ , R _202, and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.

Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used. Preferred _examples of the alkyl group and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. These groups may further have a substituent. Examples of the substituent include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

Further, when two of R ₂₀₁ to R ₂₀₃ are combined to form a ring structure, the structure represented by the following general formula (A1) is preferable.

In general formula (A1),
R ^1a to R ^13a each independently represents a hydrogen atom or a substituent.

Of R ^1a to R ^13a , 1 to 3 are preferably not hydrogen atoms, and more preferably any one of R ^9a to R ^13a is not a hydrogen atom.

Za is a single bond or a divalent linking group.

X ⁻ has the same meaning as Z ⁻ in formula (ZI).

Specific examples in the case where R ^1a to R ^13a are not a hydrogen atom include halogen atoms, linear, branched, and cyclic alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, nitro groups, and carboxyl groups. , Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, amino Carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl And arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphini Ruamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), other Known substituents are listed as examples.

In the case where R ^1a to R ^13a are not a hydrogen atom, it is preferably a linear, branched or cyclic alkyl group substituted with a hydroxyl group.

Examples of the divalent linking group for Za include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether bond, a thioether bond, an amino group, a disulfide group, and — (CH ₂ ) _N —CO—, — (CH ₂ ) _n —SO ₂ —, —CH═CH—, aminocarbonylamino group, aminosulfonylamino group and the like (n is an integer of 1 to 3).

Note that preferable structures in the case where at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0047 and 0048 of JP-A-2004-233661 and paragraphs 0040 to 340 of JP-A-2003-35948. Compounds exemplified as formulas (I-1) to (I-70) in US Patent Application Publication No. 2003 / 0224288A1, and in Formula (IA-1) of US Patent Application Publication No. 2003 / 0077540A1 ) To (IA-54) and cation structures of compounds exemplified as formulas (IB-1) to (IB-24).

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the aforementioned compound (ZI).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the aforementioned compound (ZI) may have.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In the general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.

R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkylene group, an alkenylene group or an arylene group.

Specific examples of the aryl group represented by Ar ₃ , Ar ₄ , R ₂₀₈ , R _209, and R ₂₁₀ are the same as the specific examples of the aryl group represented by R ₂₀₁ , R _202, and R ₂₀₃ in the general formula (ZI). Can be mentioned.

Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ , R ₂₀₉ and R ₂₁₀ include specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI), respectively. The same can be mentioned.

The alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 carbon atoms. To 12 alkenylene groups (for example, ethenylene group, propenylene group, butenylene group, etc.), and the arylene group of A is an arylene group having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Each can be mentioned.

Specific examples of the acid generator include those described below, for example, paragraphs 0368 to 0377 of JP-A-2014-41328, paragraphs 0240 to 0262 of JP-A-2013-228881, US Patent Application Publication No. 2015 / And those described in paragraph 0339 of the specification of 004533.

The acid generator can be used alone or in combination of two or more.

The content of the acid generator is preferably 0.1 to 50% by mass, more preferably 0.5 to 45% by mass, and further preferably 1 to 40% by mass based on the total solid content of the composition. %.

[4] Compound that decomposes by the action of an acid to generate an acid The actinic ray-sensitive or radiation-sensitive resin composition of the present invention further includes one or two compounds that decompose by the action of an acid to generate an acid. More than one species may be included. The acid generated from the compound that decomposes by the action of the acid to generate an acid is preferably a sulfonic acid, a methide acid, or an imido acid.

Examples of the compound capable of being decomposed by the action of an acid and generating an acid that can be used in the present invention include those described in JP-A-2014-41328, paragraphs 0379 to 0382, and these compounds can be used. The contents are incorporated herein.

The above-described compounds that generate an acid by the action of an acid can be used singly or in combination of two or more.

The content of the compound that decomposes by the action of an acid to generate an acid is preferably 0.1 to 40% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. The content is more preferably 0.5 to 30% by mass, and still more preferably 1.0 to 20% by mass.
[5] Resist solvent (coating solvent)
The solvent that can be used in preparing the composition is not particularly limited as long as it can dissolve each component. For example, alkylene glycol monoalkyl ether carboxylate (propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy- 2-acetoxypropane)), alkylene glycol monoalkyl ether (propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol)), lactate alkyl ester (ethyl lactate, methyl lactate, etc.), cyclic lactone (γ- Butyrolactone, preferably 4 to 10 carbon atoms, chain or cyclic ketone (2-heptanone, cyclohexanone, etc., preferably 4 to 10 carbon atoms), alkylene carbonate (ethylene carbonate, propylene, etc.) Such emission carbonate), alkyl carboxylic acids (alkyl acetate such as butyl acetate is preferred), an alkoxy alkyl acetates (ethyl ethoxypropionate), and the like, may be used those solvents alone or in combination.
Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

Of the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.

These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40.

The solvent having a hydroxyl group is preferably an alkylene glycol monoalkyl ether, and the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate.
[6] Basic compound The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a basic compound. The basic compound is preferably a compound having a stronger basicity than phenol. Moreover, this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.

Although the nitrogen-containing basic compound that can be used is not particularly limited, for example, compounds classified into the following (1) to (7) can be used.

(1) Compound represented by general formula (BS-1)

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

The carbon number of the alkyl group as R is not particularly limited, but is usually 1 to 20, preferably 1 to 12.

The carbon number of the cycloalkyl group as R is not particularly limited, but is usually 3 to 20, and preferably 5 to 15.

The number of carbon atoms of the aryl group as R is not particularly limited, but is usually 6 to 20, and preferably 6 to 10. Specific examples include a phenyl group and a naphthyl group.

The carbon number of the aralkyl group as R is not particularly limited, but is usually 7 to 20, preferably 7 to 11. Specific examples include a benzyl group.

In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.

In the compound represented by the general formula (BS-1), it is preferable that at least two of R are organic groups.

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

In addition, preferred basic compounds represented by the general formula (BS-1) include those in which at least one R is an alkyl group substituted with a hydroxy group. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.

In addition, the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specifically, for example, tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.

Examples of the basic compound represented by the general formula (BS-1) having such a hydroxyl group or an oxygen atom include the following.

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

Examples of compounds having a preferred nitrogen-containing heterocyclic structure include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and Aminoalkylmorpholine is mentioned. These may further have a substituent.

Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.

Particularly preferable basic compounds include, for example, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2 -Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2- Amino-4-methylpyridine, 2-amino5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl ) Piperazine, N- (2-aminoe) L) Piperidine, 4-amino-2,2,6,6 tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methyl Pyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5 methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, Examples include 3-pyrazoline, N-aminomorpholine and N- (2-aminoethyl) morpholine.

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

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

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

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

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

(4) Ammonium salt As the basic compound, an ammonium salt can also be used as appropriate.

The cation of the ammonium salt is preferably a tetraalkylammonium cation substituted with an alkyl group having 1 to 18 carbon atoms, such as tetramethylammonium cation, tetraethylammonium cation, tetra (n-butyl) ammonium cation, tetra (n-heptyl) ammonium. A cation, a tetra (n-octyl) ammonium cation, a dimethylhexadecylammonium cation, a benzyltrimethyl cation, and the like are more preferable, and a tetra (n-butyl) ammonium cation is most preferable.

Examples of ammonium salt anions include halides, sulfonates, borates, phosphates, hydroxides and carboxylates. Of these, hydroxide or carboxylate is particularly preferred.

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

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

Examples of the aryl group contained in the aryl sulfonate include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent. As this substituent, for example, a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms are preferable. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferred. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

The carboxylate may be an aliphatic carboxylate or an aromatic carboxylate, and examples thereof include acetate, lactate, birubate, trifluoroacetate, adamantane carboxylate, hydroxyadamantane carboxylate, benzoate, naphthoate, salicylate, phthalate, phenolate and the like. In particular, benzoate, naphthoate, phenolate and the like are preferable, and benzoate is most preferable.

In this case, the ammonium salt is preferably tetra (n-butyl) ammonium benzoate, tetra (n-butyl) ammonium phenolate, or the like.

When the ammonium salt is a hydroxide, the ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc. Tetraalkylammonium hydroxide is particularly preferred.

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

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

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

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

Specific examples of the compound (PA) include the following compounds. Furthermore, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP2014-41328A and paragraphs 0108 to 0116 of JP2014-134686A can be used. The contents of which are incorporated herein.

In the present invention, a compound (PA) other than the compound that generates the compound represented by the general formula (PA-1) can be appropriately selected. For example, an ionic compound that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

In the formula, A represents a sulfur atom or an iodine atom.

M represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.

R represents an aryl group.

R _N represents an aryl group substituted with a proton acceptor functional group.

X ⁻ represents a counter anion.

Specific examples of X ⁻ include those similar to Z— in the general formula (ZI) described above.

Specific examples of the aryl group of R and R _N is a phenyl group are preferably exemplified.

Specific examples of the proton acceptor functional group R _N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).

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

(6) Guanidine Compound The composition of the present invention may further contain a guanidine compound having a structure represented by the following formula.

The guanidine compound exhibits strong basicity because the positive charge of the conjugate acid is dispersed and stabilized by three nitrogens.

The basicity of the guanidine compound (A) of the present invention is preferably such that the pKa of the conjugate acid is 6.0 or more, and 7.0 to 20.0 is high in neutralization reactivity with the acid, It is preferable because of excellent roughness characteristics, and more preferably 8.0 to 16.0.

Because of such strong basicity, it is possible to suppress acid diffusibility and contribute to the formation of an excellent pattern shape.

Here, “pKa” means pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value, the higher the acid strength. Specifically, pKa in an aqueous solution can be actually measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the software package 1 below, A value based on a database of constants and known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

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

In the present invention, log P is a logarithmic value of n-octanol / water partition coefficient (P), and is an effective parameter that can characterize the hydrophilicity / hydrophobicity of a wide range of compounds. In general, the distribution coefficient is obtained by calculation without experimentation. In the present invention, CSChemDrawUltraVer. The value calculated by 8.0 software package (Crippen's fragmentation method) is shown.

Further, it is preferable that logP of the guanidine compound (A) is 10 or less. By being below the above value, it can be contained uniformly in the resist film.

In the present invention, the log P of the guanidine compound (A) is preferably in the range of 2 to 10, more preferably in the range of 3 to 8, and still more preferably in the range of 4 to 8.

Moreover, it is preferable that the guanidine compound (A) in this invention does not have a nitrogen atom other than a guanidine structure.
Hereinafter, although the specific example of a guanidine compound is shown, it is not limited to these.

(7) Low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid The composition of the present invention comprises a low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter referred to as “low molecular compound”) In this case, it is possible to contain “low molecular compound (D)” or “compound (D)”. The low molecular compound (D) preferably has basicity after the group capable of leaving by the action of an acid is eliminated.

The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.

The molecular weight of the low molecular compound (D) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.

The compound (D) is preferably an amine derivative having a group on the nitrogen atom that is eliminated by the action of an acid.

Compound (D) 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 general formula (d-1),
R ′ each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.

R ′ is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

The specific structure of such a group is shown below.

The compound (D) can also be constituted by arbitrarily combining the basic compound and the structure represented by the general formula (d-1).

It is particularly preferable that the compound (D) has a structure represented by the following general formula (A).

The compound (D) may correspond to the above basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.

In the general formula (A), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.

Rb each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxyalkyl group. However, in —C (Rb) (Rb) (Rb), when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.

At least two Rb may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.

N represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

In general formula (A), the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Ra and Rb are functional groups such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group and oxo group. , An alkoxy group and a halogen atom may be substituted. The same applies to the alkoxyalkyl group represented by Rb.

An alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group of Ra and / or Rb (these alkyl group, cycloalkyl group, aryl group, and aralkyl group are substituted with the above functional group, alkoxy group, or halogen atom); You may)
For example, a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., a group derived from these alkanes, for example, A group substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group,
A group derived from a cycloalkane such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, a group derived from these cycloalkanes, for example, a methyl group, an ethyl group, an n-propyl group, a group substituted with one or more linear or branched alkyl groups such as i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like,
Groups derived from aromatic compounds such as benzene, naphthalene, anthracene, etc., and groups derived from these aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 A group substituted with one or more of linear or branched alkyl groups such as -methylpropyl group, 1-methylpropyl group, t-butyl group, etc.,
Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole, benzimidazole, groups derived from these heterocyclic compounds are linear or branched A group substituted with one or more groups derived from an alkyl group or an aromatic compound, a group substituted with one or more groups, a group derived from a linear or branched alkane, or a group derived from a cycloalkane, a phenyl group, a naphthyl group Group, a group substituted with one or more groups derived from an aromatic compound such as anthracenyl group, or the like, or the above-mentioned substituent is a hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group And a group substituted with a functional group such as an oxo group.

Examples of the divalent heterocyclic hydrocarbon group (preferably having a carbon number of 1 to 20) or a derivative thereof formed by bonding of Ra to each other include pyrrolidine, piperidine, morpholine, 1, 4, 5, 6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2, , 3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2, 5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, Groups derived from heterocyclic compounds such as indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, groups derived from these heterocyclic compounds A group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino And groups substituted with one or more functional groups such as a group, a morpholino group and an oxo group.

The compound represented by the general formula (A) can be synthesized based on JP-A No. 2007-298569, JP-A No. 2009-199021 and the like.

In the present invention, the low molecular compound (D) can be used singly or in combination of two or more.

As specific examples of the particularly preferable compound (D) in the present invention, for example, those described in paragraphs 0468 to 0470 of JP-A-2014-41328 can be used, and the contents thereof are incorporated herein. .

(8) Ionic compound represented by general formula (I) The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may contain an ionic compound represented by the following general formula (I). Good.

In general formula (I),
A ⁻ represents an organic acid anion, L represents a single bond or a divalent linking group, X ⁺ represents a nitrogen cation or a sulfur cation, and Rx each independently represents an alkyl group or an aryl group. . A plurality of Rx may be bonded to each other to form a ring, and the formed ring may have a nitrogen atom, an oxygen atom or a sulfur atom as a ring member.

n2 represents 3 when X ⁺ is a nitrogen cation, and represents 2 when X ⁺ is a sulfur cation.

As for the ionic compound represented by the general formula (I), for example, the contents described in paragraphs 0167 to 0177 of JP-A-2014-199273 can be used, and these contents are incorporated in the present specification. .

The composition of the present invention may or may not contain the low molecular compound (D), but when it is contained, the content of the compound (D) is the total solid of the composition combined with the basic compound described above. The amount is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the minute.

When the composition of the present invention contains an acid generator, the ratio of the acid generator and the compound (D) used in the composition is: acid generator / [compound (D) + the following basic compound] (mole Ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / [compound (D) + basic compound] (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

In addition, examples of compounds that can be used in the composition according to the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, compounds described in Paragraph 0108 of JP-A No. 2007-298569, and the like. It is done.

As the basic compound, a photosensitive basic compound may be used. Examples of the photosensitive basic compound include JP-T-2003-524799 and J. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) and the like can be used.

The molecular weight of the basic compound is usually 100 to 1500, preferably 150 to 1300, and more preferably 200 to 1000.

These basic compounds may be used alone or in combination of two or more.

When the composition according to the present invention contains a basic compound, its content is preferably 0.01 to 8.0% by mass based on the total solid content of the composition, preferably 0.1 to The content is more preferably 5.0% by mass, and particularly preferably 0.2 to 4.0% by mass.

The molar ratio of the basic compound to the photoacid generator is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, and still more preferably 0.1-3. The photoacid generator at the molar ratio is based on the total amount of the repeating unit (B) of the resin and the photoacid generator that the resin may further contain.
[7] Hydrophobic resin (HR)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a hydrophobic resin (HR) separately from the resin (Ab).

The hydrophobic resin (HR) preferably contains a group having a fluorine atom, a group having a silicon atom, or a hydrocarbon group having 5 or more carbon atoms in order to be unevenly distributed on the film surface. These groups may be present in the main chain of the resin or may be substituted on the side chain. Specific examples of the hydrophobic resin (HR) are shown below.

As the hydrophobic resin, those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.
[8] Surfactant The composition according to the present invention may further contain a surfactant. By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.

As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.

Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. Also, F-top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); ( PF636, PF656, PF6320 or PF6520 (OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos) Good. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.

In addition to known surfactants as described above, the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

The polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate and / or (poly (oxyalkylene)) methacrylate. Even if it distributes, block copolymerization may be sufficient.

Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group. In addition, units having different chain length alkylene in the same chain, such as poly (block connection body of oxyethylene, oxypropylene, and oxyethylene) and poly (block connection body of oxyethylene and oxypropylene) Also good.

Further, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate has a monomer having two or more different fluoroaliphatic groups and two or more different (poly (oxyalkylene). )) It may be a ternary or higher copolymer obtained by copolymerizing acrylate or methacrylate simultaneously.

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC Corporation). Further, a copolymer of an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate or methacrylate, an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyethylene)) acrylate or methacrylate And a copolymer of (poly (oxypropylene)) acrylate or methacrylate, a copolymer of an acrylate or methacrylate having a C ₈ F ₁₇ group and (poly (oxyalkylene)) acrylate or methacrylate, and C ₈ F ₁₇ Of acrylate or methacrylate having a group with (poly (oxyethylene)) acrylate or methacrylate and (poly (oxypropylene)) acrylate or methacrylate Coalescence, and the like.

Further, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.

These surfactants may be used alone or in combination of two or more.

When the composition according to the present invention contains a surfactant, its content is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, based on the total solid content of the composition, More preferably, the content is 0.0005 to 1% by mass.
[9] Other additives In addition to the components described above, the composition of the present invention has a molecular weight of 3000 or less as described in carboxylic acid, carboxylic acid onium salt, Proceeding of SPIE, 2724, 355 (1996), etc. A blocking compound, a dye, a plasticizer, a photosensitizer, a light absorber, an antioxidant, and the like can be appropriately contained.

In particular, carboxylic acid is preferably used for improving the performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.

The content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 3% by mass in the total solid content of the composition.

The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably used in a film thickness of 10 to 250 nm, more preferably in a film thickness of 20 to 200 nm, from the viewpoint of improving resolution. More preferably, it is preferably used at 30 to 100 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 coating property and film forming property.

The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, more preferably 2.0. Is 5.3 mass%. By setting the solid content concentration within the above range, the resist solution can be uniformly applied on the substrate, and further, a resist pattern having excellent line width roughness can be formed. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.

The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the above components are dissolved in a predetermined organic solvent, preferably the above mixed solvent, filtered, and then applied onto a predetermined support (substrate). Use. 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 still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

<Pattern formation method>
Next, the pattern forming method of the present invention will be described.
As described above, the pattern forming method of the present invention includes:
Forming a film using an actinic ray-sensitive or radiation-sensitive resin composition;
Exposing the film,
The film after exposure is developed using a developer containing an organic solvent (organic solvent developer) to form a negative pattern in this order.

According to the pattern forming method of the present invention described above, in an ultrafine region (for example, a region having a line width or space width on the order of several tens of nanometers), high sensitivity, high resolving power when forming an isolated space pattern, and good etching resistance. At the same time, a pattern forming method, an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a method for producing an electronic device using these, and an electronic device can be provided.

The above effect is considered to be particularly remarkable when a fine pattern is formed by electron beam or extreme ultraviolet exposure.
(1) Film formation The actinic ray-sensitive or radiation-sensitive film of the present invention is a film formed from the actinic ray-sensitive or radiation-sensitive resin composition described above.

More specifically, the formation of the actinic ray-sensitive or radiation-sensitive film is performed by dissolving the above-described components of the actinic ray-sensitive or radiation-sensitive resin composition in a solvent and, if necessary, filtering through a filter. It can be performed by applying to a support (substrate). The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.5 μm or less, more preferably 0.2 μm or less, and still more preferably 0.1 μm or less.

The composition is applied onto a substrate (eg, silicon, silicon dioxide coating) used for manufacturing an integrated circuit element by an appropriate application method such as a spin coater. Thereafter, it is dried to form a photosensitive film. Heating (pre-baking) is preferably performed in the drying stage.

The film thickness is not particularly limited, but is preferably adjusted in the range of 10 to 500 nm, more preferably in the range of 10 to 200 nm, and still more preferably in the range of 10 to 100 nm. When the actinic ray-sensitive or radiation-sensitive resin composition is applied by a spinner, the rotation speed is usually 500 to 3000 rpm, preferably 800 to 2000 rpm, more preferably 1000 to 1500 rpm.

The heating (pre-baking) temperature is preferably 60 to 200 ° C., more preferably 80 to 150 ° C., and still more preferably 90 to 140 ° C.

The heating (pre-baking) time is not particularly limited, but is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds.

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

If necessary, a commercially available inorganic or organic antireflection film can be used. Further, an antireflection film can be applied to the lower layer of the actinic ray-sensitive or radiation-sensitive resin composition. As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as Brewer Science DUV30 series, DUV-40 series, Shipley AR-2, AR-3 and AR-5 may be used. it can.
(2) Exposure Exposure is performed with actinic rays or radiation. Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, extreme ultraviolet light (EUV light), and electron beams. As these actinic rays or radiation, for example, those having a wavelength of 250 nm or less, particularly 220 nm or less are more preferable. Examples of such actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, extreme ultraviolet rays (EUV light), and electron beams. Preferable actinic rays or radiations include, for example, KrF excimer laser, electron beam, X-ray and EUV light. More preferred are electron beam, X-ray and EUV light, and still more preferred are electron beam and EUV light.
(3) Baking It is preferable to perform baking (heating) after exposure and before development.

The heating temperature is preferably 60 to 150 ° C, more preferably 80 to 150 ° C, and still more preferably 90 to 140 ° C.

The heating time is not particularly limited, but is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.

The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved. Moreover, it is also preferable that a heating process (Post Bake) is included after the rinse process mentioned later. The heating temperature and heating time are as described above. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking.
(4) Development In the present invention, development is performed using a developer containing an organic solvent.
-Developer The vapor pressure of the developer (the vapor pressure as a whole in the case of a mixed solvent) is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic solvent to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. It is thought to improve.

Various organic solvents are widely used as the organic solvent used in the developer. For example, solvents such as ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, etc. Can be used.

In the present invention, the ester solvent is a solvent having an ester group in the molecule, the ketone solvent is a solvent having a ketone group in the molecule, and the alcohol solvent is alcoholic in the molecule. It is a solvent having a hydroxyl group, an amide solvent is a solvent having an amide group in the molecule, and an ether solvent is a solvent having an ether bond in the molecule. Among these, there is a solvent having a plurality of types of the above functional groups in one molecule. In that case, it corresponds to any solvent type including the functional group of the solvent. For example, diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification. Further, the hydrocarbon solvent is a hydrocarbon solvent having no substituent.

In particular, a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents and ether solvents is preferable.

Examples of ester solvents include methyl acetate, ethyl acetate, butyl acetate, pentyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy- 2-acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monophenyl ether Tate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3- Tyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, Butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, Examples include ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. Can do.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Examples include phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and γ-butyrolactone.

Examples of the alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, Alcohols such as n-octyl alcohol, n-decanol and 3-methoxy-1-butanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; alias 1 -Methoxy-2-propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbuta Glycol ethers containing hydroxyl groups such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether Examples thereof include system solvents. Among these, it is preferable to use a glycol ether solvent.

Examples of ether solvents include glycol ether solvents that contain hydroxyl groups, glycol ether solvents that do not contain hydroxyl groups such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, anisole, and phenetole. And aromatic ether solvents, dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like. Preferably, an glycol ether solvent or an aromatic ether solvent such as anisole is used.

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

Examples of the hydrocarbon solvent include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, perfluoroheptane. Aliphatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc. And aromatic hydrocarbon solvents.

The developer is an ester solvent having 7 or more carbon atoms (more preferably 7 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and still more preferably 7 to 10 carbon atoms) and a hetero atom number of 2 or less. It is preferable to use it.

The hetero atom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms is preferably 2 or less.

Preferred examples of ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, Examples thereof include butyl propionate, isobutyl isobutyrate, heptyl propionate, and butyl butanoate, and it is particularly preferable to use isoamyl acetate.

Instead of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms, the developer is a mixed solvent of the ester solvent and the hydrocarbon solvent, or the ketone solvent and the hydrocarbon. A mixed solvent of solvents may be used. Even in this case, it is effective in suppressing the swelling of the resist film.

When an ester solvent and a hydrocarbon solvent are used in combination, isoamyl acetate is preferably used as the ester solvent. As the hydrocarbon solvent, it is preferable to use a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of adjusting the solubility of the resist film.

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

The concentration of the organic solvent in the developer (total in the case of a plurality of mixtures) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. Particularly preferred is a case consisting essentially of an organic solvent. In addition, the case where it consists only of an organic solvent includes the case where a trace amount surfactant, antioxidant, stabilizer, an antifoamer, etc. are contained.

Among the above solvents, it is more preferable to contain at least one selected from the group consisting of butyl acetate, pentyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, 2-heptanone and anisole.

As the organic solvent used as the developer, an ester solvent can be preferably exemplified.

As the ester solvent, it is more preferable to use a solvent represented by the general formula (S1) described later or a solvent represented by the general formula (S2) described later, and use a solvent represented by the general formula (S1). It is even more preferred that alkyl acetate is used, and butyl acetate, pentyl acetate, and isopentyl acetate are most preferred.

R—C (═O) —O—R ′ Formula (S1)
In the general formula (S1),
R and R ′ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R and R ′ may be bonded to each other to form a ring.

The carbon number of the alkyl group, alkoxyl group and alkoxycarbonyl group for R and R ′ is preferably in the range of 1 to 15, and the carbon number of the cycloalkyl group is preferably 3 to 15.

R and R ′ are preferably a hydrogen atom or an alkyl group, and an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, and a ring formed by combining R and R ′ with respect to R and R ′, It may be substituted with a hydroxyl group, a group containing a carbonyl group (for example, an acyl group, an aldehyde group, alkoxycarbonyl, etc.), a cyano group, or the like.

Examples of the solvent represented by the general formula (S1) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, and butyl lactate. , Propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, propion Examples thereof include isopropyl acid, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and the like.

Among these, it is preferable that R and R ′ are unsubstituted alkyl groups.
The solvent represented by the general formula (S1) is preferably alkyl acetate, more preferably butyl acetate, amyl acetate (pentyl acetate), or isoamyl acetate (isopentyl acetate), and is preferably isoamyl acetate. Further preferred.

The solvent represented by the general formula (S1) may be used in combination with one or more other organic solvents. The combined solvent in this case is not particularly limited as long as it can be mixed without being separated into the solvent represented by the general formula (S1), and the solvents represented by the general formula (S1) may be used in combination. The solvent represented by the general formula (S1) may be used by mixing it with a solvent selected from other ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents. good. One or more solvents can be used in combination, but it is preferable to use one solvent in order to obtain stable performance. When mixing and using one type of combined solvent, the mixing ratio of the solvent represented by the general formula (S1) and the combined solvent is usually 20:80 to 99: 1, preferably 50:50 to 97: by mass ratio. 3, more preferably 60:40 to 95: 5, and most preferably 60:40 to 90:10.

R ″ —C (═O) —O—R ′ ″ — O—R ″ ″ Formula (S2)
In general formula (S2),
R ″ and R ″ ″ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R ″ and R ″ ″ may be bonded to each other to form a ring.

R ″ and R ′ ″ ″ are preferably a hydrogen atom or an alkyl group. The carbon number of the alkyl group, alkoxyl group and alkoxycarbonyl group for R ″ and R ″ ″ is preferably in the range of 1 to 15, and the carbon number of the cycloalkyl group is 3 to 15. Is preferred.

R ″ ″ represents an alkylene group or a cycloalkylene group. R ″ ″ is preferably an alkylene group. The number of carbon atoms of the alkylene group for R ′ ″ is preferably in the range of 1 to 10. The carbon number of the cycloalkylene group for R ″ ′ is preferably in the range of 3 to 10.

An alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group for R ″ and R ″ ″, an alkylene group, a cycloalkylene group for R ′ ″, and R ″ and R ″ ″. The ring formed by bonding to each other may be substituted with a hydroxyl group, a group containing a carbonyl group (for example, an acyl group, an aldehyde group, alkoxycarbonyl, etc.), a cyano group, or the like.

In general formula (S2), the alkylene group for R ′ ″ may have an ether bond in the alkylene chain.

Examples of the solvent represented by the general formula (S2) include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl. Ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-meth Cypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3 -Methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4 Methyl-4-methoxy-pentyl acetate and the like, is preferably a propylene glycol monomethyl ether acetate.

Among these, R ″ and R ″ ″ are preferably unsubstituted alkyl groups, R ′ ″ is preferably an unsubstituted alkylene group, and R ″ and R ″ ″ are methyl groups. And R ″ and R ″ ″ are more preferably methyl groups.

The solvent represented by the general formula (S2) may be used in combination with one or more other organic solvents. The combined solvent in this case is not particularly limited as long as it can be mixed without being separated into the solvent represented by the general formula (S2), and the solvents represented by the general formula (S2) may be used in combination. The solvent represented by the general formula (S2) may be used by mixing it with a solvent selected from other ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents. good. One or more solvents can be used in combination, but it is preferable to use one solvent in order to obtain stable performance. When mixing and using one type of combination solvent, the mixing ratio of the solvent represented by formula (S2) and the combination solvent is usually 20:80 to 99: 1, preferably 50:50 to 97: by mass. 3, more preferably 60:40 to 95: 5, and most preferably 60:40 to 90:10.

In addition, as an organic solvent used as a developer, an ether solvent can also be suitably exemplified.

Examples of the ether solvent that can be used include the ether solvents described above, and among these, an ether solvent containing one or more aromatic rings is preferable, and a solvent represented by the following general formula (S3) is more preferable. Most preferred is anisole.

In general formula (S3),
R _S represents an alkyl group. The alkyl group preferably has 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group.

In the present invention, the water content of the developer is usually 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and most preferably contains no water. preferable.
-Surfactant A developer containing an organic solvent can contain an appropriate amount of a surfactant as required.

As the surfactant, the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive resin composition described above can be used.

The amount of the surfactant used is usually from 0.001 to 5% by mass, preferably from 0.005 to 2% by mass, more preferably from 0.01 to 0.5% by mass, based on the total amount of the developer.
-Basic compound The developer containing an organic solvent may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those in the basic compound that can be contained in the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.
・ Development method As a development method, for example, the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), and the developer is developed on the surface of the substrate by surface tension and kept stationary for a certain period of time. Method (paddle method), Method of spraying developer on the substrate surface (spray method), Method of continuously discharging developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic Dispensing method) can be applied.
Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.

The development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is usually 10 seconds to 300 seconds. Preferably, it is 20 seconds to 120 seconds.

The temperature of the developer is preferably from 0 ° C to 50 ° C, more preferably from 15 ° C to 35 ° C.
(5) Rinsing The pattern forming method of the present invention may include a step of washing with a rinsing liquid containing an organic solvent after the development step. From the viewpoint of throughput, the amount of rinsing liquid used, etc., the rinsing step It is preferable not to contain.
-Rinse solution The vapor pressure of the rinse solution used after development (the vapor pressure as a whole in the case of a mixed solvent) is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less. Preferably, it is 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

As the rinsing liquid, various organic solvents are used. At least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents or It is preferable to use a rinse solution containing water.

More preferably, after the development, a step of washing with a rinse solution containing at least one organic solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent or a hydrocarbon solvent. Do. Even more preferably, after the development, a step of washing with a rinse solution containing an alcohol solvent or a hydrocarbon solvent is performed.

Particularly preferably, a rinse liquid containing at least one selected from the group of monohydric alcohols and hydrocarbon solvents is used.

Here, examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, 3-methyl- 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol , 3-octanol, 4-octanol, 3-methyl-3-pentanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol 2-methyl-3-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, -Methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-dityl-2-hexanol, 6-methyl- 2-heptanol, 7-methyl-2-octanol, 8-methyl-2-nonanol, 9-methyl-2-decanol and the like can be used, preferably 1-hexanol, 2-hexanol, 1-pentanol, 3-methyl-1-butanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, most preferably 1-hexanol or 4-methyl-2-pentanol.

As the hydrocarbon solvent, the solvents mentioned in the developer can be preferably used.

As the organic solvent contained in the rinsing liquid, when using EUV light (ExtremeExtViolet) or EB (Electron Beam) in the exposure process described later, it is preferable to use a hydrocarbon solvent among the above organic solvents. More preferably, an aromatic hydrocarbon solvent is used. As the aliphatic hydrocarbon solvent used in the rinsing liquid, an aliphatic hydrocarbon solvent having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, Hexadecane, etc.) are preferred, aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.

In addition, the upper limit of the number of carbon atoms of the aliphatic hydrocarbon solvent is not particularly limited, and examples thereof include 16 or less, preferably 14 or less, and more preferably 12 or less.

Among the above fat-side hydrocarbon solvents, decane, undecane, and dodecane are particularly preferable, and undecane is most preferable.

A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above. The solvent may be mixed with water, but the water content in the rinsing liquid is usually 60% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. is there. A favorable rinse characteristic can be acquired by making a moisture content into 60 mass% or less.

An appropriate amount of a surfactant can be contained in the rinse liquid.
As the surfactant, the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive resin composition described above can be used, and the amount used is usually 0. The content is 001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.
-Rinsing method In the rinsing step, the developed wafer is cleaned using the rinsing liquid containing the organic solvent.

The method of the cleaning process is not particularly limited. For example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary discharge method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), and the like can be applied. Among these, a cleaning process is performed by a rotary discharge method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.

The rinse time is not particularly limited, but is usually 10 to 300 seconds. The time is preferably 10 seconds to 180 seconds, and most preferably 20 seconds to 120 seconds.

The temperature of the rinse liquid is preferably 0 ° C. to 50 ° C., more preferably 15 ° C. to 35 ° C.

Further, after the developing process or the rinsing process, it is possible to perform a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid.

Furthermore, after the development processing, the rinsing processing or the processing with the supercritical fluid, a heat processing can be performed to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as a good resist pattern can be obtained, and is usually 40 ° C. to 160 ° C. The heating temperature is preferably 50 ° C. or higher and 150 ° C. or lower, and most preferably 50 ° C. or higher and 110 ° C. or lower. The heating time is not particularly limited as long as a good resist pattern can be obtained, but is usually 15 seconds to 300 seconds, and preferably 15 to 180 seconds.
Alkali development The pattern formation method of the present invention can further include a step of performing development using an aqueous alkali solution to form a resist pattern (alkali development step). Thereby, a finer pattern can be formed.

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

Alkali development can be performed either before or after the development step using a developer containing an organic solvent, but is more preferably performed before the organic solvent development step.

Examples of alkaline aqueous solutions that can be used for alkali development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and first amines such as ethylamine and n-propylamine. Secondary amines such as amines, diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxy Alkaline aqueous solutions such as quaternary ammonium salts such as copper and cyclic amines such as pyrrole and piperidine.

Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.

The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.

The pH of the alkali developer is usually from 10.0 to 15.0.

In particular, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide is desirable.

The alkali development time is not particularly limited and is usually 10 to 300 seconds. Preferably, it is 20 seconds to 120 seconds.

The temperature of the alkali developer is preferably from 0 ° C to 50 ° C, more preferably from 15 ° C to 35 ° C.

A rinse treatment can be performed after development with an alkaline aqueous solution. As the rinsing liquid in the rinsing treatment, pure water is preferable, and an appropriate amount of a surfactant can be added and used.

Further, after the development process or the rinse process, a heat treatment can be performed in order to remove moisture remaining in the pattern.

Further, the remaining developer or rinse solution can be removed by heating. The heating temperature is not particularly limited as long as a good resist pattern can be obtained, and is usually 40 ° C. to 160 ° C. The heating temperature is preferably 50 ° C. or higher and 150 ° C. or lower, and most preferably 50 ° C. or higher and 110 ° C. or lower. The heating time is not particularly limited as long as a good resist pattern can be obtained, but is usually 15 seconds to 300 seconds, and preferably 15 to 180 seconds.

For a film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, a liquid (immersion medium) having a higher refractive index than air is interposed between the film and the lens when irradiated with actinic rays or radiation. You may satisfy | fill and perform exposure (immersion exposure). Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.

The immersion liquid used for the immersion exposure will be described below.
The immersion liquid is a liquid that is transparent to the exposure wavelength and has the smallest possible temperature coefficient of refractive index so as to minimize distortion of the optical image projected on the actinic ray-sensitive or radiation-sensitive film. However, in addition to the above-mentioned viewpoints, it is preferable to use water from the viewpoints of easy availability and easy handling.

Also, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. This medium may be an aqueous solution or an organic solvent.

When water is used as the immersion liquid, the actinic ray-sensitive or radiation-sensitive film on the wafer is not dissolved and the lower surface of the lens element is not dissolved in order to reduce the surface tension of the water and increase the surface activity. An additive (liquid) that can ignore the influence on the optical coating may be added in a small proportion. The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specifically includes methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained. On the other hand, when an impurity whose refractive index is significantly different from that of water is mixed, the optical image projected on the actinic ray-sensitive or radiation-sensitive film is distorted, and distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

The electric resistance of water is preferably 18.3 MΩcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

An immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) may be provided between the film of the composition of the present invention and the immersion liquid so that the film does not directly contact the immersion liquid. Good. The functions necessary for the top coat are appropriate application to the upper layer portion of the composition film and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the composition film and can be uniformly applied to the upper layer of the composition film.

Specific examples of the top coat include hydrocarbon polymers, acrylic acid ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, fluorine-containing polymers, and the like. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

When removing the topcoat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed at the same time as the film development processing step, it is preferable that the peeling step can be performed with a developer containing an organic solvent.

The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. When water is used as the immersion liquid, the top coat is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.

It is preferable that the top coat is not mixed with the film and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Furthermore, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

On the other hand, at the time of EUV exposure or EB exposure, the actinic ray sensitivity or sensation of the present invention is used for the purpose of suppressing outgas, the purpose of suppressing blob defects, the deterioration of collapse due to improved reverse taper shape, and the deterioration of LWR due to surface roughness. A topcoat layer may be formed on the actinic ray-sensitive or radiation-sensitive film formed from the radiation-sensitive resin composition. Hereinafter, the topcoat composition used for forming the topcoat layer will be described.
In the top coat composition of the present invention, the solvent is preferably water or an organic solvent. More preferred is water or an alcohol solvent.
When the solvent is an organic solvent, it is preferably a solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film. As the solvent that can be used, an alcohol solvent, a fluorine solvent, or a hydrocarbon solvent is preferably used, and a non-fluorine alcohol solvent is more preferably used. As the alcohol solvent, a primary alcohol is preferable from the viewpoint of applicability, and a primary alcohol having 4 to 8 carbon atoms is more preferable. As the primary alcohol having 4 to 8 carbon atoms, a linear, branched or cyclic alcohol can be used, but a linear or branched alcohol is preferred. Specific examples include 1-butanol, 1-hexanol, 1-pentanol and 3-methyl-1-butanol.

When the solvent of the topcoat composition in the present invention is water, an alcohol solvent or the like, it is preferable to contain a water-soluble resin. By containing a water-soluble resin, it is considered that the uniformity of solubility in a developer can be further improved. Preferred water-soluble resins include polyacrylic acid, polymethacrylic acid, polyhydroxystyrene, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl ether, polyvinyl acetal, polyacrylimide, polyethylene glycol, polyethylene oxide, polyethyleneimine, polyester polyol and polyether polyol. , Polysaccharides, and the like. Particularly preferred are polyacrylic acid, polymethacrylic acid, polyhydroxystyrene, polyvinylpyrrolidone, and polyvinyl alcohol. The water-soluble resin is not limited to a homopolymer, and may be a copolymer. For example, it may be a copolymer having monomers corresponding to the repeating units of the homopolymers listed above and other monomer units. Specifically, acrylic acid-methacrylic acid copolymer, acrylic acid-hydroxystyrene copolymer and the like can also be used in the present invention.

Further, as the resin for the top coat composition, resins having an acidic group described in JP-A-2009-134177 and JP-A-2009-91798 can be preferably used.

The weight average molecular weight of the water-soluble resin is not particularly limited, but is preferably 2,000 to 1,000,000, more preferably 5,000 to 500,000, and particularly preferably 10,000 to 100,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

The pH of the top coat composition is not particularly limited, but is preferably 0 to 10, more preferably 0 to 8, and particularly preferably 1 to 7.

When the solvent of the topcoat composition is an organic solvent, the topcoat composition contains a hydrophobic resin such as the hydrophobic resin (HR) described above in the actinic ray-sensitive or radiation-sensitive resin composition section. You may do it. As the hydrophobic resin, it is also preferable to use a hydrophobic resin described in JP-A-2008-209889.
The concentration of the resin in the top coat composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.3 to 3% by mass.

The topcoat material may contain components other than the resin, but the ratio of the resin to the solid content of the topcoat composition is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably Is from 95 to 100% by weight.

The solid content concentration of the top coat composition in the present invention is preferably 0.1 to 10, more preferably 0.2 to 6% by mass, and further preferably 0.3 to 5% by mass. preferable. By making solid content concentration into the said range, a topcoat composition can be uniformly apply | coated on actinic-light sensitive or radiation sensitive film | membrane.

Components other than the resin that can be added to the topcoat material include surfactants, photoacid generators, basic compounds, and the like. Specific examples of the photoacid generator and the basic compound include compounds that generate an acid upon irradiation with actinic rays or radiation and compounds similar to the basic compound.

When a surfactant is used, the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the topcoat composition.

By adding a surfactant to the topcoat composition, the coating property when applying the topcoat composition can be improved. Surfactants include nonionic, anionic, cationic and amphoteric surfactants.

Nonionic surfactants include BALF's Plufrac series, Aoki Yushi Kogyo's ELEBASE series, Finesurf series, Braunon series, Asahi Denka Kogyo's Adeka Pluronic P-103, Kao Chemical's Emulgen Series, Amit series, Aminone PK-02S, Emanon CH-25, Rheodor series, Surflon S-141 from AGC Seimi Chemical Co., Neugen series from Daiichi Kogyo Seiyaku, New Calgen series from Takemoto Yushi DYNOL604 manufactured by Nissin Chemical Industry Co., Ltd., Envirogem AD01, Orphine EXP series, Surfynol series, Footage 300 manufactured by Hishie Chemical Co., etc. can be used.

As anionic surfactant, Kao Chemical's Emar 20T, Poise 532A, TOHO's Phosphanol ML-200, Clariant Japan's EMULSOGEN series, AGC Seimi Chemical's Surflon S-111N, Surflon S -211, Daiichi Kogyo Seiyaku's Prisurf series, Takemoto Yushi Co., Ltd. Pionein series, Nissin Chemical Industry Co., Ltd. Orphine PD-201, Olphin PD-202, Nippon Surfactant Kogyo Co., Ltd. AKYPO RLM45, ECT -3, Lion manufactured by Lion, etc. can be used.

As the cationic surfactant, Acetamine 24, Acetamine 86, etc. manufactured by Kao Chemical Co., Ltd. can be used.
As an amphoteric surfactant, Surflon S-131 (manufactured by AGC Seimi Chemical Co., Ltd.), Enajicol C-40H, Lipomin LA (manufactured by Kao Chemical Co., Ltd.) or the like can be used.

Also, these surfactants can be mixed and used.

In the pattern forming method of the present invention, an actinic ray-sensitive or radiation-sensitive film can be formed on the substrate using the actinic ray-sensitive or radiation-sensitive resin composition, and the actinic ray-sensitive or radiation-sensitive film is formed. A top coat layer can be formed on the top coat composition. The film thickness of the actinic ray-sensitive or radiation-sensitive film is preferably 10 to 100 nm, and the film thickness of the topcoat layer is preferably 10 to 200 nm, more preferably 20 to 100 nm, and particularly preferably 40 to 80 nm. It is.

As a method of applying the actinic ray-sensitive or radiation-sensitive resin composition on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater. Dry to form an actinic ray-sensitive or radiation-sensitive film. In addition, a known antireflection film can be applied in advance. Moreover, it is preferable to dry the actinic ray-sensitive or radiation-sensitive film before forming the topcoat layer.

Next, on the obtained actinic ray-sensitive or radiation-sensitive film, a topcoat composition is applied and dried by the same means as the method for forming an actinic-ray-sensitive or radiation-sensitive film, and a topcoat layer is formed. can do.

The actinic ray-sensitive or radiation-sensitive film having a top coat layer as an upper layer is usually irradiated with an electron beam (EB), X-ray or EUV light through a mask, and preferably baked (heated) and developed. Thereby, a good pattern can be obtained.
[Usage]
The pattern forming method of the present invention is suitably used for the production of semiconductor microcircuits such as the manufacture of VLSI and high-capacity microchips. When creating a semiconductor microcircuit, the actinic ray-sensitive or radiation-sensitive film having a pattern formed thereon is subjected to circuit formation or etching, and the remaining actinic ray-sensitive or radiation-sensitive film portion is finally Is removed with a solvent or the like, so that the final product such as a microchip is derived from the actinic ray-sensitive or radiation-sensitive resin composition described in the present invention, unlike so-called permanent resists used for printed boards and the like. No actinic ray-sensitive or radiation-sensitive film remains.

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

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

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not limited by this.
<Synthesis of Resin (Ab)>
Synthesis Example 1: Synthesis of Resin (Ab-5) 9.16 g of a 50.00 mass% cyclohexanone solution of Compound (1), 7.22 g of Compound (2), 2.59 g of Compound (3), 5 .60 g of compound (4) and 2.92 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 43.40 g of cyclohexanone. 11.99 g of cyclohexanone was placed in the reaction vessel and dropped into the system at 85 ° C. in a nitrogen gas atmosphere over 4 hours. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.
The reaction solution was diluted by adding 20 g of ethyl acetate and dropped into 1000 g of heptane to precipitate the polymer, followed by filtration. The filtered solid was washed with 300 g of heptane. Then, the solution which added 80 g of ethyl acetate to the filtered solid was dripped in 1000 g of heptane, the polymer was precipitated, and it filtered. The filtered solid was washed with 300 g of heptane. Thereafter, the washed solid was subjected to vacuum drying to obtain 9.60 g of resin (Ab-5).

The obtained resin (Ab-5) was measured by GPC (carrier: tetrahydrofuran (THF)), weight average molecular weight (Mw: converted to polystyrene), number average molecular weight (Mn: converted to polystyrene), and dispersity (Mw / Mn, Hereinafter, “Pd”) was calculated. Further, the composition ratio (molar ratio) was calculated by ¹ H-NMR (Nuclear Magnetic Resonance) and ¹³ C-NMR measurement.

The same operations as in Synthesis Example 1 were performed to synthesize the following resins Ab-1 to A-4 and A-6 to A-37 as the resin (Ab).

[Comparative resin]
The following resins were used as comparative resins.

Hereinafter, the photoacid generator, the basic compound, the hydrophobic resin, the surfactant, the solvent, the developing solution and the rinsing solution used in Examples and Comparative Examples are shown.
[Photoacid generator]
The photoacid generator was appropriately selected from the acid generators z1 to z30 listed above.
[Basic compounds]

[Hydrophobic resin]

[Surfactant]
W-1: Megafuck R08 (Dainippon Ink & Chemicals, Inc .; fluorine and silicon)
W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
W-3: Troisol S-366 (manufactured by Troy Chemical Co., Ltd .; fluorine-based)
W-4: PF6320 (manufactured by OMNOVA; fluorine-based)
〔solvent〕
S-1: Propylene glycol monomethyl ether acetate (PGMEA) (boiling point = 146 ° C.)
S-2: Propylene glycol monomethyl ether (PGME) (boiling point = 120 ° C.)
S-3: Ethyl lactate (boiling point = 155 ° C.)
S-4: Cyclohexanone (boiling point = 157 ° C.).
[Developer / Rinse solution]
G-1: Butyl acetate G-2: 2-Heptanone G-3: Anisole G-4: Isoamyl acetate G-5: TMAH; 2.38 mass% tetramethylammonium hydroxide aqueous solution G-6: 4-methyl-2 -Pentanol G-7: 1-Hexanol G-8: Undecane G-9: Water <EB exposure>
(1) Coating solution preparation and coating of actinic ray-sensitive or radiation-sensitive resin composition The components shown in Table 1 below are dissolved in a solvent shown in the same table by 3.0% by mass in solid content, and each is 0.1 μm. Microfiltration was performed with a membrane filter having a pore size to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) solution.

This actinic ray-sensitive or radiation-sensitive resin composition solution was applied onto a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and 100 ° C. for 60 seconds. It dried on the hotplate and obtained the resist film with a film thickness of 100 nm.

(2) EB exposure and development The wafer coated with the resist film obtained in (1) above was subjected to pattern irradiation using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). . At this time, drawing was performed so that a 1: 1 line and space was formed. After the electron beam drawing, the sample was heated on a hot plate at 100 ° C. for 90 seconds, then padded with an organic developer described in Table 1 and developed for 30 seconds. The rinse was performed using the rinse solution described in 1. Next, the wafer was rotated at 4000 rpm for 30 seconds and then heated at 95 ° C. for 60 seconds to obtain a 1: 1 line and space resist pattern having a line width of 100 nm.
(3) Evaluation of resist pattern The obtained resist pattern was evaluated for the resolution and etching resistance of the isolated space pattern by the following method.

<Resolving power in isolated space pattern>
Irradiation energy when resolving a pattern with a line width of 100 nm: space = 1: 1 is sensitivity (Eop), and the limit resolution (line and space) of the isolated space pattern (line: space => 100: 1) in the above Eop The minimum line width at which the space is separated and resolved) was determined. This value was defined as “resolving power of isolated space pattern (nm)”. The smaller this value, the better the performance. The results are shown in Table 1. <Etching resistance>
In the coating liquid adjustment and coating of the above (1) actinic ray-sensitive or radiation-sensitive resin composition, a resist film having a film thickness of 200 nm is formed, and then C ₄ F ₆ (20 mL / min) and O ₂ (40 mL / min) are formed. plasma etching was performed for 30 seconds under the condition of a temperature of 23 ° C. Thereafter, the remaining film amount was determined, and the etching rate was calculated. And etching resistance was evaluated based on the following criteria. The results are shown in Table 1.
(Criteria)
A: When the etching rate is less than 1 nm / second B: When the etching rate is 1 nm / second or more and less than 1.5 nm / second C: When the etching rate is 1.5 nm / second or more [Other matters]
When the alkaline developer (G-5) is used, pattern exposure is performed using an exposure mask obtained by inverting the pattern of the exposure mask, and the alkaline developer (G-5) is used instead of the organic developer. The resist composition was prepared and patterned in the same manner as described above, and the resist pattern was evaluated. The results are shown in Table 1.

<EUV exposure>
(4) Coating solution preparation and coating of actinic ray-sensitive or radiation-sensitive resin composition The components shown in Table 2 below are dissolved in a solvent shown in the same table by 1.5% by mass in solid content, and each is 0.05 μm. Microfiltration was performed with a membrane filter having a pore size to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) solution.
This actinic ray-sensitive or radiation-sensitive resin composition solution was applied onto a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and 100 ° C. for 60 seconds. It dried on the hotplate and obtained the resist film with a film thickness of 50 nm.
(5) EUV exposure and development The wafer coated with the resist film obtained in the above (4) is subjected to an EUV exposure apparatus (Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0, manufactured by Exitech) .36) and pattern exposure was performed using an exposure mask (line / space = 1/1). After exposure, after heating at 100 ° C. for 90 seconds on a hot plate, paddle the organic developer shown in Table 2 and develop for 30 seconds. Except for some examples and comparative examples, listed in Table 2. The rinsing solution was used for rinsing. Next, after rotating the wafer for 30 seconds at a rotation speed of 4000 rpm, baking was performed at 95 ° C. for 60 seconds to obtain a 1: 1 line and space pattern resist pattern having a line width of 50 nm.

(6) Evaluation of resist pattern The obtained resist pattern was evaluated for the resolution and etching resistance of the isolated space pattern by the following method. <Resolving power in isolated space pattern>
Irradiation energy when resolving a line: space = 1: 1 pattern having a line width of 50 nm is sensitivity (Eop), and the limiting resolution (line and space) of the isolated space pattern (line: space = 5: 1) in the above Eop. (Minimum line width for separating and resolving). This value was defined as “resolution (nm)”. The smaller this value, the better the performance. The results are shown in Table 2. <Etching resistance>
In the coating liquid adjustment and coating of the above (4) actinic ray-sensitive or radiation-sensitive resin composition, a resist film having a film thickness of 200 nm is formed, and then C ₄ F ₆ (20 mL / min) and O ₂ (40 mL / min) are formed. plasma etching was performed for 30 seconds under the condition of a temperature of 23 ° C. Thereafter, the remaining film amount was determined, and the etching rate was calculated. And etching resistance was evaluated based on the following criteria. The results are shown in Table 2.
(Criteria)
A: When the etching rate is less than 1 nm / second B: When the etching rate is 1 nm / second or more and less than 1.5 nm / second C: When the etching rate is 1.5 nm / second or more [Other matters]
When the alkaline developer (G-5) is used, pattern exposure is performed using an exposure mask obtained by inverting the pattern of the exposure mask, and the alkaline developer (G-5) is used instead of the organic developer. The resist composition was prepared and patterned in the same manner as described above, and the resist pattern was evaluated. The results are shown in Table 2.

Claims

An actinic ray-sensitive or radiation-sensitive resin containing at least a resin (Ab) containing a repeating unit represented by the following general formula (Ab1) as a repeating unit having a group that decomposes by the action of an acid to generate a polar group Forming a film using the composition;
Exposing the film; and
The pattern formation method including the process of developing the film | membrane after exposure using the developing solution containing an organic solvent, and forming a negative pattern.

Where
A 11 represents a hydrogen atom or a substituent, A 12 represents a single bond or a divalent aromatic ring group, A 13 represents a hydrogen atom or a substituent, and L 11 represents a single bond or a divalent group. Represents a linking group, R 11 represents a group capable of leaving by the action of an acid, and r 11 represents an integer of 1 or more.
However, at least one of A 11 and A 12 represents an aromatic ring group. When A 12 is an aromatic ring group, L 11 represents a divalent linking group, and an atom directly bonded to A 12 in the linking group in this case is not an oxygen atom.
The pattern formation method of Claim 1 whose repeating unit represented by general formula (Ab1) is a repeating unit represented by the following general formula (Ab2).

Where
R 21 represents a group capable of leaving by the action of an acid, R 22 represents a substituent, L 21 represents a single bond or a divalent linking group, and p 21 represents 0 or an integer of 1 or more. Q 21 represents 0 or an integer of 1 or more.
The pattern formation method of Claim 1 whose repeating unit represented by general formula (Ab1) is a repeating unit represented by the following general formula (Ab3).

Where
R 31 represents a group capable of leaving by the action of an acid, R 32 represents a substituent, L 31 represents a divalent linking group, A 31 represents a hydrogen atom or a substituent, and A 33 Represents a hydrogen atom or a substituent, p 31 represents 0 or an integer of 1 or more, q 31 represents 0 or an integer of 1 or more, and r 31 represents an integer of 1 or more.
However, in the divalent linking group represented by L 31 , the atom directly bonded to the aromatic ring group in the formula is not an oxygen atom.
The pattern forming method according to any one of claims 1 to 3, wherein the resin (Ab) further has a repeating unit represented by the following general formula (A).

Where
R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R 42 may form a ring with Ar 4 or X 4, R 42 in this case represents a single bond or an alkylene group.
X 4 represents a single bond, an alkylene group, —COO—, or —CONR 64 —. Here, R 64 represents a hydrogen atom or an alkyl group.
L 4 represents a single bond, —COO—, or an alkylene group.
Ar 4 represents an (n + 1) -valent aromatic ring group, and when bonded to R 42 to form a ring, represents an (n + 2) -valent aromatic ring group.
n represents an integer of 1 to 4.
The group which is eliminated by the action of an acid represented by R 11 in the general formula (Ab1) is a group represented by the following general formula (ALG1) or (ALG2). The pattern forming method according to item.

In general formula (ALG1),
R 1 and R 3 each independently represent a hydrogen atom or a substituent, and R 2 represents a substituent. R 1 and R 2 may be bonded to each other to form a ring.
In general formula (ALG2),
R 4 , R 5 and R 6 each independently represents an alkyl group or a cycloalkyl group. Two selected from R 4 , R 5 and R 6 may be bonded to each other to form a ring.
6. The pattern forming method according to claim 1, wherein the exposure is exposure with an electron beam or extreme ultraviolet rays.
The pattern forming method according to any one of claims 1 to 6, wherein the actinic ray-sensitive or radiation-sensitive resin composition further comprises a compound that generates an acid upon irradiation with actinic rays or radiation.
Forming a film using an actinic ray-sensitive or radiation-sensitive resin composition;
A step of exposing the film, and a step of developing the exposed film using a developer containing an organic solvent to form a negative pattern,
An actinic ray-sensitive or radiation-sensitive resin composition used in a pattern forming method comprising:
An actinic ray-sensitive or radiation-sensitive resin containing at least a resin (Ab) containing a repeating unit represented by the following general formula (Ab1) as a repeating unit having a group that decomposes by the action of an acid to generate a polar group Composition.

Where
A 11 represents a hydrogen atom or a substituent, A 12 represents a single bond or a divalent aromatic ring group, A 13 represents a hydrogen atom or a substituent, and L 11 represents a single bond or a divalent group. Represents a linking group, R 11 represents a group capable of leaving by the action of an acid, and r 11 represents an integer of 1 or more.
However, at least one of A 11 and A 12 represents an aromatic ring group. When A 12 is an aromatic ring group, L 11 represents a divalent linking group, and an atom directly bonded to A 12 in the linking group in this case is not an oxygen atom.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8, wherein the repeating unit represented by the general formula (Ab1) is a repeating unit represented by the following general formula (Ab2).

Where
R 21 represents a group capable of leaving by the action of an acid, R 22 represents a substituent, L 21 represents a single bond or a divalent linking group, and p 21 represents 0 or an integer of 1 or more. Q 21 represents 0 or an integer of 1 or more.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8, wherein the repeating unit represented by the general formula (Ab1) is a repeating unit represented by the following general formula (Ab3).

Where
R 31 represents a group capable of leaving by the action of an acid, R 32 represents a substituent, L 31 represents a divalent linking group, p 31 represents 0 or an integer of 1 or more, and A 31 31 represents a hydrogen atom or a substituent, A 33 represents a hydrogen atom or a substituent, q 31 represents 0 or an integer of 1 or more, and r 31 represents an integer of 1 or more.
However, in the divalent linking group represented by L 31 , the atom directly bonded to the aromatic ring group in the formula is not an oxygen atom.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 8 to 10, wherein the resin (Ab) further has a repeating unit represented by the following general formula (A).

Where
R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R 42 may form a ring with Ar 4 or X 4, R 42 in this case represents a single bond or an alkylene group.
X 4 represents a single bond, an alkylene group, —COO—, or —CONR 64 —. Here, R 64 represents a hydrogen atom or an alkyl group.
L 4 represents a single bond, —COO—, or an alkylene group.
Ar 4 represents an (n + 1) -valent aromatic ring group, and when bonded to R 42 to form a ring, represents an (n + 2) -valent aromatic ring group.
n represents an integer of 1 to 4.
The group represented by the following general formula (ALG1) or (ALG2) is a group capable of leaving by the action of an acid represented by R 11 in the general formula (Ab1). The actinic ray-sensitive or radiation-sensitive resin composition according to Item.

In general formula (ALG1),
R 1 and R 3 each independently represent a hydrogen atom or a substituent, and R 2 represents a substituent. R 1 and R 2 may be bonded to each other to form a ring.
In general formula (ALG2),
R 4 , R 5 and R 6 each independently represents an alkyl group or a cycloalkyl group. Two selected from R 4 , R 5 and R 6 may be bonded to each other to form a ring.
An actinic ray-sensitive or radiation-sensitive film comprising the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 8 to 12.
An electronic device manufacturing method including the pattern forming method according to any one of claims 1 to 7.