JPWO2019044547A1 - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and electronic device manufacturing method - Google Patents

Abstract

Provided is an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in resolution and shape characteristics of a formed pattern even when applied to a thick film application. Further, the present invention provides a resist film, a pattern forming method, and a method for manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition is a negative type composition used for forming a pattern having a film thickness of 1 μm or more, and includes a compound represented by the general formula (ZI-3) and a general formula At least one acid generator selected from the group consisting of compounds represented by (ZI-4), a cross-linking agent, a resin containing a reactive group capable of reacting with the cross-linking agent; And at least one resin selected from the group consisting of resins containing a structure protected by a leaving group that decomposes and leaves.

Description

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

Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as a resist image forming method in order to compensate for a decrease in sensitivity due to light absorption. For example, as a positive type chemical amplification image forming method, a photoacid generator in an exposed portion is decomposed by exposure to an excimer laser, an electron beam, extreme ultraviolet light or the like to generate an acid, and a post-exposure bake (PEB) : Post Exposure Bake), the generated acid is used as a reaction catalyst to change an alkali-insoluble group into an alkali-soluble group, and an exposed portion is removed with an alkali developing solution.
As such a resist composition, for example, Patent Document 1 describes a positive resist composition containing a resin having a p-hydroxystyrene-based repeating unit.

JP 2000-147772 A

On the other hand, at present, miniaturization using the wavelength of an exposure light source is approaching its limit. In particular, in an implantation process step and a NAND memory (NOT AND memory), a three-dimensional memory layer is mainly used for the purpose of increasing the capacity. It is becoming. Since increasing the number of processing steps in the vertical direction is required to make the memory layer three-dimensional, the resist film is required to be thicker from a conventional nano-size to a micron-size.
The present inventors prepared a thick (1 μm or more) resist film using a positive resist composition containing a resin having a p-hydroxystyrene-based repeating unit described in Patent Document 1, and exposed and developed the resist film. When the performance of the pattern was examined, it was clarified that the resolution and shape characteristics were not always sufficient, and there was room for further improvement.

Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in resolution and shape characteristics of a formed pattern even when applied to a thick film application.
Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.

The present inventors have conducted intensive studies to achieve the above object, and as a result, a negative actinic ray-sensitive or radiation-sensitive resin composition containing an acid generator having a predetermined structure can solve the object of the present invention. And completed the present invention.
That is, the inventors have found that the above-described object can be achieved by the following configuration.

[1] A negative-type actinic ray-sensitive or radiation-sensitive resin composition having a thickness of 1 μm or more, which is used for forming a pattern.
At least one acid generator selected from the group consisting of a compound represented by the following general formula (ZI-3) and a compound represented by the following general formula (ZI-4),
A crosslinking agent,
At least one selected from the group consisting of a repeating unit containing a reactive group capable of reacting with the cross-linking agent and a repeating unit containing a structure protected by a leaving group which is decomposed and eliminated by the action of an acid; An actinic ray-sensitive or radiation-sensitive resin composition comprising: a resin having a kind of repeating unit.
[2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], which is used for forming a pattern having a thickness of 1 to 100 µm.
[3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], which forms a pattern by being exposed to light having an absorption wavelength of 248 nm or more.
[4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin is an alkali-soluble resin.
[5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin contains a phenolic hydroxyl group.
[6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the resin contains a repeating unit represented by the general formula (I).
[7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the resin further contains a repeating unit represented by the general formula (3).
[8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the crosslinking agent is a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in a molecule. Stuff.
[9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the cross-linking agent contains two or more compounds having two or more alkoxymethyl groups in a molecule. .
[10] A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9].
[11] a resist film forming step of forming a resist film having a thickness of 1 μm or more using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9];
An exposure step of exposing the resist film,
A developing step of developing the exposed resist film using a developing solution.
[12] A method for manufacturing an electronic device, including the pattern forming method according to [11].

According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in resolution and shape characteristics of a formed pattern even when applied to a thick film application.
Further, according to the present invention, it is possible to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

As used herein, the term “actinic ray” or “radiation” refers to, for example, an emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-ray, and electron beam (EB). : Electron Beam). As used herein, “light” means actinic rays or radiation.
The term “exposure” in the present specification means, unless otherwise specified, the emission line spectrum of a mercury lamp, far ultraviolet light represented by excimer laser, extreme ultraviolet light, X-ray, and EUV light, as well as electron beam, and This also includes drawing by a particle beam such as an ion beam.
In this specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit and an upper limit.

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

In the description of the group (atomic group) in the present specification, the notation of not indicating substituted or unsubstituted includes a group having a substituent as well as a group having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the “organic group” in the present specification refers to a group containing at least one carbon atom.
Examples of the substituent include a monovalent nonmetallic atomic group excluding a hydrogen atom, and for example, can be selected from the following substituent group T.
(Substituent T)
As the substituent T, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group An alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; an alkyl group; a cycloalkyl group Aryl group, heteroaryl group, hydroxyl group, carboxy group, formyl group, sulfo group, cyano group, alkylaminocarbonyl group, arylaminocarbonyl group, sulfonamide group, silyl group, amino group, monoalkylamino group, dialkylamino group; Arylamino groups; and combinations thereof.

(Actinic ray-sensitive or radiation-sensitive resin composition)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also simply referred to as “composition of the present invention”) is used for forming a pattern having a film thickness of 1 μm or more. Or a radiation-sensitive resin composition,
At least one acid generator selected from the group consisting of a compound represented by the following general formula (ZI-3) and a compound represented by the following general formula (ZI-4),
A crosslinking agent,
At least one resin selected from the group consisting of a resin containing a reactive group capable of reacting with the crosslinking agent, and a resin containing a structure protected by a leaving group which is decomposed and eliminated by the action of an acid; And a resin.
The composition of the present invention is typically a chemically amplified resist composition.

According to the actinic ray-sensitive or radiation-sensitive resin composition having the above configuration, the composition has excellent resolution and excellent shape characteristics (in other words, has a high aspect ratio (aspect ratio: height / line width); A pattern having a rectangular cross-section) can be formed.
This is not clear in detail, but is presumed as follows.
In general, as the thickness of a resist film (actinic ray-sensitive or radiation-sensitive film) to be formed is larger, light does not reach a deep portion of the film during exposure, and the resolution and shape characteristics of a formed pattern are increased. Worsens.
In contrast, the present inventors have found that when forming a pattern with a resist film having a film thickness of 1 μm or more, the resist film is formed of a negative-type actinic ray-sensitive or radiation-sensitive resin composition. It has been found that a pattern having more excellent resolution can be formed as compared with the case where a positive actinic ray-sensitive or radiation-sensitive resin composition is used. Further, the above-mentioned acid generator contained in the composition of the present invention allows light to easily reach a deep part of the film during exposure due to its structural characteristics. It is considered that the effects of the present invention were obtained by synergistic effects of the above-mentioned mechanism of action.
Hereinafter, the components contained in the composition of the present invention will be described in detail.

<Acid generator (A)>
The composition of the present invention contains at least one acid generator selected from the group consisting of a compound represented by the following general formula (ZI-3) and a compound represented by the following general formula (ZI-4).
The compound represented by the following general formula (ZI-3) and the compound represented by the following general formula (ZI-4) will be described below.

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

The alkyl group represented by R _{1c to} R _5c (including both linear and branched chains) preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group.
The cycloalkyl group represented by R _{1c to} R _5c preferably has 3 to 15 carbon atoms, and more preferably 3 to 10 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and a norbornyl group.
The aryl group represented by R _{1c to} R _5c is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
The alkoxy group represented by R _{1c to} R _5c preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a sec-butoxy group, and a t-butoxy group.
The aryloxy group represented by R _{1c to} R _5c preferably has 6 to 14 carbon atoms, and specific examples include a phenyloxy group and a naphthyloxy group.
The alkoxycarbonyl group represented by R _{1c to} R _5c preferably has 2 to 15 carbon atoms, and more preferably 2 to 10 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butoxycarbonyl group, a sec-butoxycarbonyl group, and a t-butoxycarbonyl group.
The alkylcarbonyloxy group represented by R _{1c to} R _5c preferably has 2 to 15 carbon atoms, and more preferably 2 to 10 carbon atoms. Specific examples include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, and a t-butylcarbonyloxy group.
The cycloalkylcarbonyloxy group represented by R _{1c to} R _5c preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms. Specific examples include a cyclopropylcarbonyloxy group, a cyclobutylcarbonyloxy group, and a cyclohexylcarbonyloxy group.
Examples of the halogen atom represented by R _{1c to} R _5c include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkylthio group represented by R _{1c to} R _5c preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. Specific examples include a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, a sec-butylthio group, and a t-butylthio group.
The arylthio group represented by R _{1c to} R _5c preferably has 6 to 14 carbon atoms. Specific examples include a phenylthio group and a naphthylthio group.

The alkyl group, cycloalkyl group, halogen atom and aryl group represented by R _6c and R _7c have the same meanings as the alkyl group, cycloalkyl group, halogen atom and aryl group represented by R _{1c to} R _5c. Yes, and the preferred embodiment is also the same.

The alkyl group and cycloalkyl group represented by R _x and R _y, the same meaning as the alkyl group and cycloalkyl group represented by R _1c to R _5c, a preferred embodiment is also the same.
The 2-oxoalkyl group represented by R _x and R _y preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. Specific examples include a 2-oxopropyl group and a 2-oxobutyl group.
The 2-oxocycloalkyl group represented by R _x and R _y preferably has 3 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples include a 2-oxocyclohexyl group.
The alkoxycarbonylalkyl group represented by R _x and R _y preferably has 3 to 15 carbon atoms, and more preferably 3 to 10 carbon atoms. Specific examples include an ethoxycarbonylmethyl group.

_{R 1c} ~R _7c, R _x, and _{R y} may further have a substituent. Examples of the substituent include those exemplified in the above-described substituent group T.

In the general formula (ZI-3), any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y are each Independently, they may be bonded to each other to form a ring, and the ring may contain an oxygen atom, a sulfur atom, a carbonyl group, an ester bond, or an amide bond.

  Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic structure obtained by combining two or more of these rings. Ring condensed rings are exemplified. The ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

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

The R _1c to R _5c, in that the resolution and the shape characteristics of the pattern to be formed more excellent hydrogen atom, an alkyl group, a cycloalkyl group, or an alkoxy group, _or the R 1c _{to R 5c} It is preferable that any two of them are bonded to each other to form an alicyclic structure containing an oxygen atom (preferably a 6-membered ring). Among them, R _3c is preferably an alkyl group, a cycloalkyl group, or an alkoxy group, and R _1c , R _2c , R _4c , and R _5c are preferably hydrogen atoms.
As R _6c and R _7c , a hydrogen atom or an alkyl group is preferable in that the resolution and shape characteristics of the formed pattern are more excellent, and it is more preferable that at least one of R _6c and R _7c is an alkyl group. preferable.
As R _x and R _y , it is preferable that R _x and R _y combine with each other to form an alicyclic structure, since the formed pattern has better resolution and shape characteristics. In addition, the said alicyclic structure contains the sulfur atom in the said General formula (ZI-3). The alicyclic structure is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

  As the cation in the general formula (ZI-3), for example, the cation described in paragraphs <0036> and after of US Patent Application Publication No. 2012/0076996 is also included in the embodiment of the present invention.

Zc ^- represents an anion.
Zc ^- The non-nucleophilic anion is preferred.
Examples of the non-nucleophilic anion include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

The non-nucleophilic anion is an anion having a remarkably low ability to cause a nucleophilic reaction, and an anion capable of suppressing the decomposition with time due to an intramolecular nucleophilic reaction. This improves the stability over time of the composition.
Examples of the sulfonic acid anion include an aliphatic sulfonic acid anion, an aromatic sulfonic acid anion, and a camphorsulfonic acid anion.
Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkyl carboxylate anion.

The aliphatic site in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and may be an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms. Is preferred.
As the aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylate anion, an aryl group having 6 to 14 carbon atoms is preferable, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonic acid anion and the aromatic sulfonic acid anion may have a substituent.
Other non-nucleophilic anions include, for example, fluorinated phosphorus (eg, PF ₆ ⁻ ), fluorinated boron (eg, BF ₄ ⁻ ), and fluorinated antimony (eg, SbF ₆ ⁻ ).

Zc ^- the non-nucleophilic anion, at least α-position by an aliphatic sulfonate anion substituted with a fluorine atom, a fluorine atom or a fluorine atom is substituted by a group containing an aromatic sulfonate anion of a sulfonic acid, an alkyl group Is preferably a bis (alkylsulfonyl) imide anion substituted with a fluorine atom or a tris (alkylsulfonyl) methide anion substituted with a fluorine atom. Above all, a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms or a benzenesulfonic acid anion containing a fluorine atom is more preferable, and nonafluorobutanesulfonic acid anion, perfluorooctanesulfonic acid anion, and pentafluorobenzenesulfonic acid are preferable. Anions or 3,5-bis (trifluoromethyl) benzenesulfonic acid anions are more preferred.

Also, Zc ^- as the non-nucleophilic anion, the anion is also preferably represented by the following general formula (3).

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

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

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

L represents a divalent linking group, and when a plurality of L are present, L may be the same or different.
Examples of the divalent linking group include -COO-(-C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-,- SO -, - SO ₂ -, an alkylene group (preferably having 1 to 6 carbon atoms), a hetero atom (e.g., oxygen atom and nitrogen atom etc.,) contain also good cycloalkylene group (preferably having from 3 to 10 carbon atoms ), An alkenylene group (preferably having 2 to 6 carbon atoms) or a divalent linking group obtained by combining a plurality of these groups. Among these, -COO -, - OCO -, - CONH -, - NHCO -, - CO -, - O -, - SO 2 -, - alkylene group -COO -, - COO- alkylene group -, - alkylene group --OCO -, - OCO- alkylene group -, - SO ₂ - which may contain a hetero atom cycloalkylene group -COO- alkylene group -, - CONH- alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO ₂ -, - alkylene group -COO -, - COO- alkylene group -, - OCO- alkylene group -, - OCO- alkylene group -, or -SO ₂ - A cycloalkylene group -COO-alkylene group- which may contain a hetero atom is more preferred.

W represents an organic group containing a cyclic structure. Among them, a cyclic organic group is preferable.
Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Above all, an alicyclic group containing a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is PEB (heat after exposure). It is preferable from the viewpoints of suppressing the diffusivity in the film in the process and improving MEEF (Mask Error Enhancement Factor).

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group and an anthryl group. Of these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.
The heterocyclic group may be monocyclic or polycyclic, but polycyclic is more capable of suppressing acid diffusion. Further, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, a piperidine ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, a piperidine ring, or a decahydroisoquinoline ring.

  The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be straight-chain or branched, and preferably has 1 to 12 carbon atoms) and a cycloalkyl group (which may be any of a monocyclic, polycyclic, and spiro ring). Often having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid. Ester groups are mentioned. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

  o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

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

In the general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group containing a cycloalkyl group.
R ₁₄ represents a group containing a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group, when a plurality of groups are present, Represents
R ₁₅ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group.
R _{13 to} R ₁₅ may further have a substituent. Examples of the substituent include those exemplified in the above-described substituent group T.
In addition, two R ₁₅ may be bonded to each other to form a ring, and the ring may include a hetero atom such as an oxygen atom and a nitrogen atom. In one aspect, it is preferred that two R ₁₅ are alkylene groups and combine with each other to form a ring structure (preferably a 5-membered ring).
l represents an integer of 0 to 2.
r represents an integer of 0 to 8.
Z ^- represents an anion.

In Formula (ZI-4), the alkyl group, cycloalkyl group, alkoxy group, and alkoxycarbonyl group represented by R ₁₃ and R ₁₄ include R _{1c to} R _5c in Formula (ZI-3). It has the same meaning as the alkyl group, cycloalkyl group, alkoxy group, and alkoxycarbonyl group represented, and the preferred embodiment is also the same.
In Formula (ZI-4), as the alkyl group and cycloalkyl group represented by R ₁₅ , the alkyl group and cycloalkyl group represented by R _{1c to} R _5c in Formula (ZI-3) And the preferred embodiment is also the same.

In the general formula (ZI-4), examples of the group containing a cycloalkyl group represented by R ₁₃ and R ₁₄ include a group represented by the following general formula (4).
General formula (4) -L ₁₁ -Y ₁₁
In the general formula (4), L ₁₁ represents a single bond or a divalent linking group. Y ₁₁ represents a cycloalkyl group.
Examples of the divalent linking group represented by _{L 11,} for example, -CO -, - NH -, - O -, - S -, - SO -, - SO 2 -, an alkylene group (having 1 to 6 carbon atoms Is preferred), or a group obtained by combining two or more kinds selected from the group consisting of:
Among them, -O-alkylene group- or -alkylene group -O- is preferable.
The cycloalkyl group represented by Y ₁₁ has the same meaning as the cycloalkyl group represented by R ₁₃ , and the preferred embodiment is also the same.

In Formula (ZI-4), the alkylcarbonyl group represented by R ₁₄ preferably has 2 to 15 carbon atoms, and more preferably 2 to 10 carbon atoms. Specific examples include a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, an n-butylcarbonyl group, a sec-butylcarbonyl group, and a t-butylcarbonyl group.

In Formula (ZI-4), the alkylsulfonyl group represented by R ₁₄ preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an n-butylsulfonyl group, a sec-butylsulfonyl group, and a t-butylsulfonyl group.

In Formula (ZI-4), the cycloalkylsulfonyl group represented by R ₁₄ preferably has 3 to 15 carbon atoms, and more preferably 3 to 10 carbon atoms. Specific examples include a cyclopropylsulfonyl group, a cyclobutylsulfonyl group, a cyclohexylsulfonyl group, and a norbornylsulfonyl group.

  Examples of the cation of the compound represented by the general formula (ZI-4) include paragraphs <0121>, <0123>, and <0124> of JP-A-2010-256842, and paragraph <of JP-A-2011-76056. And cations described in <0129>, <0129>, and <0130>.

In formula (ZI-4), Z ^- represents an anion. Z ^- is, general formula (ZI-3) in Zc ^- in the above formula, preferred embodiments are also the same.

The molecular weight of the acid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
The acid generator can be synthesized by a known method, for example, according to the method described in JP-A-2007-161707.

The acid generator may be used alone or in combination of two or more.
In the composition of the present invention, the content of the acid generator (when a plurality of types are present, the total thereof) is preferably from 1 to 35% by mass, more preferably from 1 to 30% by mass, based on the total solid content of the composition. preferable.

<Crosslinking agent (B)>
The composition of the present invention contains a crosslinking agent.
The crosslinking agent is intended to be a compound containing a crosslinkable group capable of crosslinking a resin. The crosslinking agent is preferably a compound that crosslinks the resin by the action of an acid.

The crosslinkable group is not particularly limited, and examples thereof include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, and an oxetane ring. These crosslinkable groups react with reactive groups such as hydroxyl groups contained in the resin.
As the crosslinkable group, a hydroxymethyl group, an alkoxymethyl group, an oxirane ring, or an oxetane ring is preferred, a hydroxymethyl group or an alkoxymethyl group is more preferred, and an alkoxymethyl group is still more preferred.

  The crosslinking agent is preferably a compound containing two or more crosslinkable groups in the molecule, more preferably a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in the molecule. The upper limit of the crosslinkable group is not particularly limited, but typically includes 6 or less in the molecule.

  As the crosslinking agent, a phenol derivative, a urea compound (a compound having a urea structure), or a melamine compound (a compound having a melamine structure) having a crosslinkable group is preferable.

  Examples of the crosslinking agent include, in addition to the crosslinking agents described above, paragraphs <0379> to <0431> of U.S. Patent Application Publication 2016 / 0147154A1 and paragraph <0064> of U.S. Patent Application Publication 2016 / 0282720A1. Known compounds disclosed in <0141> can be used.

  The molecular weight of the crosslinking agent is not particularly limited, but is preferably 100 to 2,000, and more preferably 100 to 1200, in that the effect of the present invention is more excellent.

The crosslinking agents may be used alone or in combination of two or more.
In the composition of the present invention, the content of the crosslinking agent (when a plurality of types are present, the total thereof) is preferably from 1 to 65% by mass, more preferably from 3 to 60% by mass, based on the total solid content of the composition. , 5 to 50% by mass.

<Resin (C)>
The composition of the present invention comprises a repeating unit containing a reactive group capable of reacting with a crosslinking agent, and a repeating unit containing a structure protected by a leaving group which is decomposed and eliminated by the action of an acid. It includes a resin having at least one type of repeating unit selected from the group (hereinafter, also referred to as “resin (C1)”).
As the resin (C1), a resin having a repeating unit containing a reactive group capable of reacting with a crosslinking agent is preferable, and a resin having a repeating unit containing a structure in which a reactive group capable of reacting with a crosslinking agent is protected with a protecting group. Is also preferred.

  Examples of the main skeleton of the resin (C1) include a novolak resin, a (meth) acrylic resin, a styrene resin, and a styrene / (meth) acryl copolymer.

The reactive group capable of reacting with the crosslinking agent is appropriately selected depending on the crosslinking agent contained in the composition of the present invention, and includes, for example, a hydroxyl group, a polymerizable ethylenically unsaturated group, and a ring polymerizable group. Examples of the polymerizable ethylenically unsaturated group include an acryloyl group, a methacryloyl group, and a vinyl group. Examples of the ring polymerizable group include an oxiranyl group and an oxetanyl group. In addition, a reactive group (particularly, a hydroxyl group) capable of reacting with a crosslinking agent may be protected by a leaving group which is decomposed and eliminated by the action of an acid.
Among them, a phenolic hydroxyl group is preferable as the reactive group.
In the present specification, the phenolic hydroxyl group is a group obtained by replacing a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, such as a benzene ring and a naphthalene ring.

The resin (C1) is preferably an alkali-soluble resin containing at least one group (acid group) for promoting alkali solubility in the molecule. The acid group is not particularly limited.
The phenolic hydroxyl group described above functions as a reactive group, but also has a function as an acid group.

  As the resin (C1), a resin containing a phenolic hydroxyl group is preferable, and a resin containing a repeating unit (a1) containing a phenolic hydroxyl group is more preferable.

  The repeating unit (a1) containing a phenolic hydroxyl group includes, for example, a repeating unit represented by the following general formula (I).

In the formula (I),
R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₄₂ may combine with Ar ₄ to form a ring, in which case R ₄₂ represents a single bond or an alkylene group.
X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or a divalent linking group.
Ar ₄ represents an (n + 1) -valent aromatic hydrocarbon group, and represents an (n + 2) -valent aromatic hydrocarbon group when bonded to R ₄₂ to form a ring.
n represents an integer of 1 to 5.
For the purpose of increasing the polarity of the repeating unit represented by the general formula (I), it is also preferable that n is an integer of 2 or more, or X ₄ is —COO— or —CONR ₆₄ —.

Examples of the alkyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, which may have a substituent. A sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, an alkyl group having 20 or less carbon atoms such as a dodecyl group is preferable, an alkyl group having 8 or less carbon atoms is more preferable, and an alkyl group having 3 or less carbon atoms is preferable. More preferred.

The cycloalkyl group represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) may be monocyclic or polycyclic. A monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent is preferable.
Examples of the halogen atom represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
As the alkyl group contained in the alkoxycarbonyl group represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I), the same alkyl groups as those described above for R ₄₁ , R ₄₂ and R ₄₃ are preferable.

  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, acyl groups , An acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group and the like, and the substituent preferably has 8 or less carbon atoms.

Ar ₄ represents an (n + 1) -valent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group when n is 1 may have a substituent, for example, arylene having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group. Group, or, for example, a hetero ring such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring. Preferred are aromatic hydrocarbon groups containing.

Specific examples of the (n + 1) -valent aromatic hydrocarbon group in the case where n is an integer of 2 or more include, from the above-described specific examples of the divalent aromatic hydrocarbon group, (n-1) arbitrary arbitrary groups. A group obtained by removing a hydrogen atom is preferably exemplified.
The (n + 1) -valent aromatic hydrocarbon group may further have a substituent.

Examples of the substituent which the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group and (n + 1) -valent aromatic hydrocarbon group may have include, for example, R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I). The above-mentioned alkyl groups; alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group; aryl groups such as phenyl group;
As Ar ₄ , an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent is preferable, and a benzene ring group, a naphthalene ring group, or a biphenylene ring group is more preferable. Among them, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar ₄ is preferably a benzene ring group.

_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom or an alkyl group) The alkyl group for _{R 64} in, which may have a substituent, a methyl group, an ethyl group, a propyl group , An isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and an alkyl group having 20 or less carbon atoms such as a dodecyl group, and an alkyl group having 8 or less carbon atoms is more preferable. .
X ₄ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.

As the divalent linking group as L ₄ , an alkylene group is preferable, and as the alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group which may have a substituent are preferable. And an alkylene group having 1 to 8 carbon atoms such as

  Hereinafter, specific examples of the repeating unit (a1) containing a phenolic hydroxyl group are shown, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

  As the repeating unit (a1) containing a phenolic hydroxyl group, a repeating unit represented by the following general formula (1) is preferable.

In the general formula (1), R ₁ represents a hydrogen atom or an alkyl group.
Ar represents a divalent aromatic hydrocarbon group.

In Formula (1), the alkyl group represented by R ₁ has the same meaning as the alkyl group represented by R ₄₁ in Formula (I), and the preferred embodiments are also the same.
In the general formula (1), the divalent aromatic hydrocarbon group represented by Ar has the same meaning as the divalent aromatic hydrocarbon group represented by Ar ₄ in the general formula (I).

Further, the phenolic hydroxyl group in the resin (C1) may have a structure protected by a leaving group which is decomposed and eliminated by the action of an acid.
Examples of the leaving group that is decomposed and eliminated by the action of an acid include groups represented by formulas (Y1) to (Y4).
Formula (Y1): -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ )
Formula _{(Y2): - C (=} O) OC (Rx 1) (Rx 2) (Rx 3)
Formula _{(Y3): - C (R} 36) (R 37) (OR 38)
Formula (Y4): -C (Rn) (H) (Ar)

In formulas (Y1) and (Y2), Rx _{1 to} Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx _{1 to} Rx ₃ are an alkyl group (linear or branched), at least two of Rx _{1 to} Rx ₃ are preferably a methyl group.
Among them, Rx _{1 to} Rx ₃ are more preferably each independently a repeating unit representing a linear or branched alkyl group, and Rx _{1 to} Rx ₃ are each independently a linear unit. More preferably, it is a repeating unit representing an alkyl group.
Two of Rx _{1 to} Rx ₃ may combine to form a monocyclic or polycyclic ring.
As the alkyl group of Rx _{1 to} Rx ₃ , 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, and a t-butyl group is preferable. .
As the cycloalkyl group of Rx _{1 to} Rx ₃ , a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic ring such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group Are preferred.
Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl. And a polycyclic cycloalkyl group such as an adamantyl group. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ is, for example, a group in which one of methylene groups constituting a ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
A group represented by formula (Y1) and (Y2) is, for example, Rx ₁ is a methyl group or an ethyl group, a mode of combining and the Rx ₂ and Rx ₃ form a cycloalkyl radical as defined above preferable.

In the formula (Y3), R ₃₆ and R ₃₇ each independently represent a hydrogen atom or a monovalent organic group. R ₃₈ represents a monovalent organic group. R ₃₇ and R ₃₈ may combine with each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R ₃₆ is preferably a hydrogen atom.

  In the formula (Y4), Ar represents an aromatic hydrocarbon group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may combine with each other to form a non-aromatic ring. Ar is preferably an aryl group.

Hereinafter, an embodiment in which the resin (C1) has a repeating unit (a2) including a structure in which a phenolic hydroxyl group is protected by a leaving group which is decomposed and desorbed by the action of an acid and which is eliminated will be described as an example.
As the repeating unit (a2), those having a structure in which a hydrogen atom in a phenolic hydroxyl group is protected by a leaving group represented by formulas (Y1) to (Y4) are preferable.

  As the repeating unit (a2), a repeating unit represented by the following general formula (AII) is preferable.

In the general formula (AII),
R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, and in that case, R ₆₂ represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic hydrocarbon group, and represents an (n + 2) -valent aromatic hydrocarbon group when bonded to R ₆₂ to form a ring.
Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group which is eliminated by the action of an acid. The group capable of leaving by the action of an acid as Y ₂ is preferably any of formulas (Y1) to (Y4).
n represents an integer of 1 to 4.

As preferred embodiments of R ₆₁ , R ₆₂ , R ₆₃ , X ₆ , L ₆ , Ar ₆ and n in the general formula (AII), R ₄₁ , R ₄₂ , R ₄₃ in the above general formula (I) The same as X ₄ , L ₄ , Ar ₄ and n.
Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and Examples thereof include an alkoxycarbonyl group (2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferable.

  Hereinafter, specific examples of the repeating unit (a2) having a structure in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and eliminated by the action of an acid are shown, but the present invention is not limited thereto. .

The resin (C1) may have one type of the repeating unit (a1) containing a phenolic hydroxyl group, or may have two or more types of the repeating units (a1).
In addition, the resin (C1) may have a single type of repeating unit (a2) containing a structure in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and eliminated by the action of an acid, Two or more kinds may be used in combination.

  In the resin (C1), a repeating unit (a1) containing a phenolic hydroxyl group and / or a repeating unit (a2) containing a structure protected by a leaving group which is decomposed and eliminated by the action of an acid. The amount (in the case of including a plurality of types, the total thereof) is preferably from 10 to 100 mol%, more preferably from 30 to 97 mol%, and even more preferably from 45 to 95 mol%, based on all repeating units in the resin (C1). More preferred.

The resin (C1) further includes a repeating unit (a1) other than a repeating unit (a1) containing a phenolic hydroxyl group and a repeating unit (a2) containing a structure protected by a leaving group that is decomposed and eliminated by the action of an acid. And a repeating unit (a3) containing an aromatic hydrocarbon group.
The repeating unit (a3) containing an aromatic hydrocarbon group is not particularly limited, but is more excellent in dissolution accelerating property, and as a result, more excellent in resolution and shape characteristics. Are preferred.

In Formula (2), R ₂₁ , R ₂₂ , and R ₂₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₂₂ may combine with Ar ₁ to form a ring, and in that case, R ₂₂ represents a single bond or an alkylene group.
X ₁₁ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₁₁ represents a single bond or a divalent linking group.
Ar ₁ is, (m + 1) -valent aromatic ring _group, in the case of combining with _{R 22} form a ring represents a (m + 2) -valent aromatic ring group.
R ₂₄ each independently represent an alkyl group, a halogen atom, or represents -O-X _A group, X _A represents a group containing a polycyclic alicyclic structure of non-acid-decomposable.
m is an integer of 0 or more.

In the general formula (2), R ₂₁ , R ₂₂ , R ₂₃ , X ₁₁ , and L ₁₁ have the same meanings as R ₄₁ , R ₄₂ , R ₄₃ , X ₄ , and L _{4 in the} general formula (I), respectively. And the preferred embodiment is also the same.

In the general formula (2), Ar ₁ represents a (m + 1) -valent aromatic ring group. Examples of the aromatic ring group include an aromatic hydrocarbon group and an aromatic heterocyclic group which may have a substituent. Among them, an aromatic hydrocarbon group is preferable, a benzene ring group, a naphthalene ring group, or a biphenylene ring group is more preferable, and a benzene ring group is still more preferable. Examples of the substituent which the aromatic ring group may have include, for example, the alkyl groups mentioned for R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I); a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxy group An alkoxy group such as a propoxy group and a butoxy group; an aryl group such as a phenyl group;

In the general formula _{(2), R 24} each independently represents an alkyl group, a halogen atom, or _{-O-X A} group.
The alkyl group represented by R _24, a substituent methyl group which may have a ethyl group, a propyl group, an isopropyl group, t- butyl group, n- butyl group, sec- butyl group, a hexyl group, Alkyl groups having 20 or less carbon atoms, such as 2-ethylhexyl, octyl, and dodecyl, are preferred.
Examples of the halogen atom represented by R ₂₄ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.
In _{-O-X A} group represented by R _{24, X A} represents a group containing a polycyclic alicyclic structure of non-acid-decomposable.

Here, “non-acid-decomposable” means not decomposed or eliminated by the action of an acid. As the _{X A,} for example, preferably a group represented by the following general formula (2a).
The general formula _(2a) -L _{22 -Y} 22
In the general formula _{(2a), L 22} represents a divalent linking group. Y ₂₂ represents a polycyclic aliphatic hydrocarbon group.
Examples of the divalent linking group represented by _{L 22,} for example, a carbonyl group, a thiocarbonyl group, an alkylene group (preferably having from 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group, -COCH ₂ -, - NH-, or these combined divalent linking group (preferably having a total carbon number of 1 to 20, more preferably a total 10 carbon atoms), and carbonyl group, -COCH ₂ -, a sulfonyl group , -CONH-, or -CSNH- more preferably, a carbonyl group, or -COCH ₂ - more preferably, a carbonyl group is particularly preferred.
Y ₂₂ represents a polycyclic aliphatic hydrocarbon group and is non-acid-decomposable. The total carbon number of the polycyclic aliphatic hydrocarbon group is preferably from 5 to 40, and more preferably from 7 to 30. The polycyclic aliphatic hydrocarbon group may have an unsaturated bond in the ring.
Such a polycyclic aliphatic hydrocarbon group is a group containing a plurality of monocyclic alicyclic hydrocarbon groups or a polycyclic alicyclic hydrocarbon group, and may be a bridged type. As the monocyclic alicyclic hydrocarbon group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Note that some of the carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom. Further, the group containing a plurality of monocyclic alicyclic hydrocarbon groups preferably contains a plurality of the above cycloalkyl groups having 3 to 8 carbon atoms. Further, the group containing a plurality of monocyclic alicyclic hydrocarbon groups preferably contains 2 to 4 monocyclic alicyclic hydrocarbon groups, and more preferably contains 2 monocyclic alicyclic hydrocarbon groups.
Examples of the polycyclic alicyclic hydrocarbon group include groups having 5 or more carbon atoms, such as bicyclo, tricyclo, or tetracyclo structures, and a group having a polycyclic cyclo structure having 6 to 30 carbon atoms is preferable. Examples include an adamantyl group, a norbornyl group, a norbornenyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetracyclododecyl group, and an androstanyl group. In addition, some carbon atoms in the polycyclic cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.

Examples of the polycyclic aliphatic hydrocarbon groups of Y _22, a plurality adamantyl group, a decalin group, a norbornyl group, a norbornenyl group, a cedrol group, a plurality a group having a cyclohexyl group, a group having a plurality of cycloheptyl group, a cyclooctyl group A group having a plurality of cyclodecanyl groups, a group having a plurality of cyclododecanyl groups, or a tricyclodecanyl group, and an adamantyl group is more preferable in that dry etching resistance is more excellent.

  As the repeating unit represented by the following general formula (2), the repeating unit represented by the following general formula (3) is more preferred in that the dissolution accelerating property is more excellent, and as a result, the resolution and the shape characteristics are more excellent. preferable.

In the general formula (3), R ₂₃ represents a hydrogen atom or an alkyl group.
X _A represents a group containing a polycyclic alicyclic structure of non-acid-decomposable.
Ar ₁ represents a (m + 1) -valent aromatic ring group.
m is an integer of 1 or more.

In the general formula (3), the alkyl group represented by R ₂₃ has the same meaning as R ₂₃ in the general formula (2), preferred embodiments are also the same.
In the general formula (3), _{X A,} and Ar ₁ are each the same meaning as _{X A,} and Ar ₁ in the general formula (2), preferred embodiments are also the same.

  Hereinafter, specific examples of the repeating unit (a3) containing an aromatic hydrocarbon group will be shown, but the present invention is not limited thereto. Rx represents a hydrogen atom or an alkyl group. Note that the repeating units shown below correspond to the repeating units represented by the general formula (2).

In the resin (C1), the content of the repeating unit (a3) containing an aromatic hydrocarbon group (when plural kinds are contained, the sum thereof) is 1 to 40 mol based on all the repeating units in the resin (C1). %, More preferably 1 to 30 mol%, even more preferably 2 to 30 mol%.
When the repeating unit (a3) containing an aromatic hydrocarbon group contains the repeating unit represented by the general formula (3), the content of the repeating unit represented by the general formula (3) (including plural types) In such a case, the total) is preferably 1 to 100 mol%, more preferably 1 to 90 mol%, even more preferably 5 to 60 mol%, based on the repeating unit (a3) containing the aromatic hydrocarbon group.

  The weight average molecular weight of the resin (C1) is preferably from 1,000 to 200,000, more preferably from 2,000 to 30,000, and still more preferably from 3,000 to 25,000. The dispersity (Mw / Mn) is usually from 1.0 to 3.0, preferably from 1.0 to 2.6, more preferably from 1.0 to 2.0, and still more preferably from 1.1 to 2.0. preferable.

As the resin (C1), one type may be used alone, or two or more types may be used in combination.
In the composition of the present invention, the content of the resin (C1) is preferably from 20 to 99% by mass, more preferably from 30 to 99% by mass, and still more preferably from 40 to 99% by mass, based on the total solid content.
The composition of the present invention may further contain a resin other than the resin (C1).
The content of the resin (C1) is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 99.5% by mass or more based on the total mass of the resin.

<Acid diffusion controller (D)>
The composition of the present invention preferably contains an acid diffusion controller (D). The acid diffusion controller (D) traps an acid generated from a photoacid generator or the like at the time of exposure, and acts as a quencher that suppresses a crosslinking reaction of the resin in an unexposed portion due to excess generated acid. For example, a basic compound (DA), a basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation, an onium salt (DC) which becomes a weak acid relatively to an acid generator, a nitrogen atom And a low molecular weight compound (DD) having a group capable of leaving by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in a cation portion can be used as an acid diffusion controller. In the composition of the present invention, a known acid diffusion controller can be appropriately used. For example, paragraphs <0627> to <0664> of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs <0095> to <0187> of U.S. Patent Application Publication 2015 / 0004544A1, and U.S. Patent Application Publication 2016 / 0237190A1. Known compounds disclosed in paragraphs <0403> to <0423> of the specification and paragraphs <0259> to <0328> of U.S. Patent Application Publication 2016 / 02744458A1 are suitable as the acid diffusion controller (D). Can be used for

  As the basic compound (DA), a compound having a structure represented by the following formulas (A) to (E) is preferable.

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

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

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

  A basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter, also referred to as “compound (DB)”) has a proton acceptor functional group, and It is a compound that is decomposed by irradiation with radiation to decrease or disappear the proton acceptor property, or change from the proton acceptor property to acidic.

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

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

The compound (DB) is decomposed by irradiation with actinic rays or radiation to reduce or eliminate the proton acceptor property, or generate a compound changed from the proton acceptor property to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to acidic is a change in the proton acceptor property due to the addition of a proton to the proton acceptor functional group. Means that when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in the chemical equilibrium of the adduct is reduced.
The proton acceptor property can be confirmed by performing pH measurement.

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

  The acid dissociation constant pKa indicates an acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution. Alternatively, a value based on a database of Hammett's substituent constants and known literature values can be obtained by calculation using the following software package 1. All the pKa values described in this specification indicate values calculated by using this software package.

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

In the composition of the present invention, an onium salt (DC) which becomes a weak acid relatively to the photoacid generator can be used as an acid diffusion controller.
When a photoacid generator and an onium salt that generates an acid that is relatively weak with respect to the acid generated from the photoacid generator are used as a mixture, the photoacid generator is activated or irradiated with radiation. When the acid generated from collides with an unreacted onium salt having a weak acid anion, the weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

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

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

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

An onium salt (DC) which becomes a relatively weak acid with respect to a photoacid generator has a compound in which a cation site and an anion site are in the same molecule, and a cation site and an anion site are connected by a covalent bond ( Hereinafter, it may be referred to as “compound (DCA)”.
As the compound (DCA), a compound represented by any of the following formulas (C-1) to (C-3) is preferable.

In the general formulas (C-1) to (C-3),
R ₁ , R ₂ , and R ₃ each independently represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond linking a cation site and an anion site.
-X ^{- _{is, -COO -, -SO 3 -,}} -SO 2 -, -O -, and ^-N - represents an anion portion selected from -R _4. R ₄ represents a carbonyl group (—C (＝ O) —), a sulfonyl group (—S (＝ O) ₂ —), and a sulfinyl group (—S (＝ O) — ) Represents a monovalent substituent having at least one of the above.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may combine with each other to form a ring structure. In Formula (C-3), two of R _{1 to} R ₃ together represent one divalent substituent, and may be bonded to an N atom by a double bond.

Examples of the substituent having 1 or more carbon atoms in R _{1 to} R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino. A carbonyl group and an arylaminocarbonyl group. Preferably, it is an alkyl group, a cycloalkyl group, or an aryl group.

L ₁ as a divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, Examples include groups formed by combining at least two or more species. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

A low molecular compound (DD) having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter, also referred to as “compound (DD)”) has a group capable of leaving by the action of an acid on the nitrogen atom. Preferably, the amine derivative has
The group which is eliminated by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and more preferably a carbamate group, or a hemiaminal ether group. .
The molecular weight of the compound (DD) is preferably from 100 to 1,000, more preferably from 100 to 700, and still more preferably from 100 to 500.
Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protective group constituting the carbamate group is represented by the following general formula (d-1).

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

As R _b , a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group, or a cycloalkyl group is more preferable.
Examples of the ring formed by two R _b 's being connected to each other include an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring, a heterocyclic hydrocarbon ring, and derivatives thereof.
The specific structure of the group represented by the general formula (d-1) includes, but is not limited to, the structure disclosed in paragraph <0466> of U.S. Patent Publication US2012 / 0135348A1.

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

In the general formula (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
_Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When 1 is 2, the two _Ras may be the same or different, and the two _Ras may be mutually connected to form a heterocyclic ring with the nitrogen atom in the formula. This heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.
R _b has the same meaning as R _b in formula (d-1), and preferred examples are also the same.
In the general formula (6), the alkyl group as R _a, a cycloalkyl group, an aryl group and aralkyl group, is each independently an alkyl group as R _b, cycloalkyl group, aryl group and aralkyl group, is substituted The group which may be substituted may be substituted with the same group as described above.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of R _a (these groups may be substituted with the above group) include the same groups as those described above for R _b. Is mentioned.
Specific examples of the particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph <0475> of U.S. Patent Application Publication No. 2012 / 0135348A1.

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter, also referred to as “compound (DE)”) is preferably a compound having a basic site containing a nitrogen atom in the cation portion. The basic site is preferably an amino group, and more preferably an aliphatic amino group. More preferably, all of the atoms adjacent to the nitrogen atom in the basic site are a hydrogen atom or a carbon atom. Further, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly connected to the nitrogen atom.
Preferred specific examples of the compound (DE) include, but are not limited to, the compounds disclosed in paragraph <0203> of U.S. Patent Application Publication No. 2015 / 0309408A1.

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

In the composition of the present invention, the acid diffusion controller (D) may be used alone or in combination of two or more.
When the composition of the present invention contains an acid diffusion control agent (D), the content of the acid diffusion control agent (D) in the composition (when there are plural kinds thereof, the total thereof) is determined by the total solid content of the composition. As a reference, 0.01 to 10% by mass is preferable, and 0.03 to 5% by mass is more preferable.

<Solvent (E)>
The composition of the present invention preferably contains a solvent.
In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs <0210> to <0235> of U.S. Patent Application Publication No. 2015 / 0004544A1, and U.S. Patent Application Publication No. 2016 / 0237190A1. Known solvents disclosed in paragraphs <0424> to <0426> of the specification and paragraphs <0357> to <0366> of U.S. Patent Application Publication No. 2016 / 02744458A1 can be suitably used.
Solvents that can be used when preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), Organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate are exemplified.

As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used.
As the solvent having a hydroxyl group and the solvent having no hydroxyl group, the above-described exemplified compounds can be appropriately selected. As the solvent having a hydroxyl group, alkylene glycol monoalkyl ether or alkyl lactate is preferable, and propylene glycol monomethyl ether ( PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. Further, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, a monoketone compound which may have a ring, a cyclic lactone, or an alkyl acetate is preferable. Propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferable, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate , Cyclohexanone, cyclopentanone or 2-heptanone are more preferred. As a solvent having no hydroxyl group, propylene carbonate is also preferable.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group to the solvent having no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. preferable. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable from the viewpoint of coating uniformity.

<Surfactant (F)>
When the composition of the present invention contains a surfactant that preferably contains a surfactant, a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, Or a surfactant having both a fluorine atom and a silicon atom).

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

These surfactants may be used alone or in combination of two or more.
When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 3% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. preferable.

<Other additives>
The composition of the present invention may further contain an acid proliferating agent, a dye, a plasticizer, a photosensitizer, a light absorber, a dissolution inhibitor, a dissolution promoter, and the like.

<Preparation method>
The solid content concentration of the composition of the present invention is usually preferably from 1.0 to 50% by mass, more preferably from 10 to 50% by mass, and still more preferably from 30 to 50% by mass. The solid content concentration is a mass percentage of the mass of the other resist components excluding the solvent with respect to the total mass of the composition.

The thickness of the actinic ray-sensitive or radiation-sensitive film composed of the composition of the present invention is 1 μm or more, and is preferably 3 μm or more, more preferably 5 μm or more, and further preferably 10 μm or more for the purpose of increasing the number of processing steps. preferable. The upper limit is not particularly limited, but is, for example, 100 μm or less.
In addition, as described later, a pattern can be formed from the composition of the present invention.
The film thickness of the formed pattern is 1 μm or more, and is preferably 3 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more for the purpose of increasing the number of processing steps. The upper limit is not particularly limited, but is, for example, 100 μm or less.

  The composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering this, and then coating it on a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. This filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (JP-A-2002-62667), cyclic filtration may be performed, and a plurality of types of filters may be connected in series or in parallel. And filtration may be performed. The composition may be filtered a plurality of times. Further, the composition may be subjected to a degassing treatment before and after the filtration.

The composition of the present invention preferably has a viscosity of 100 to 500 mPa · s. The viscosity of the composition of the present invention is more preferably 100 to 300 mPa · s from the viewpoint of more excellent coating properties.
The viscosity can be measured with an E-type viscometer.

<Application>
The composition of the present invention relates to a negative type actinic ray-sensitive or radiation-sensitive resin composition which changes its properties in response to irradiation with actinic ray or radiation. More specifically, the composition of the present invention can be used for manufacturing a semiconductor such as an IC (Integrated Circuit), a circuit board such as a liquid crystal or a thermal head, manufacturing a mold structure for imprinting, and other photofabrication processes. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition. The pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, a MEMS (Micro Electro Mechanical Systems), or the like.

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

The pattern forming method of the present invention comprises:
(I) Step of forming a resist film (actinic ray-sensitive or radiation-sensitive film) having a thickness of 1 μm or more on a support with the above-described actinic ray-sensitive or radiation-sensitive resin composition (resist film forming step) ,
(Ii) exposing the resist film (irradiating actinic rays or radiation) (exposure step); and
(Iii) developing the exposed resist film using a developer (developing step);
Having.

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

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

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

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

  There is no limitation on the wavelength of the light source used in the exposure step, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-ray, and electron beam. Among these, light having an absorption wavelength of 248 nm or more is preferable, and a KrF excimer laser (248 nm) is more preferable.

  (Iii) In the development step, development using an alkaline developer is performed.

As the alkali developer, usually, a quaternary ammonium salt represented by tetramethylammonium hydroxide is used. Can be used.
Further, the alkaline developer may contain an appropriate amount of alcohols and / or a surfactant. 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 to 15.
The development time using the alkali developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.

  As a developing method, for example, a method in which a substrate is immersed in a bath filled with a developing solution for a certain period of time (dip method), a method in which the developing solution is raised on the substrate surface by surface tension and is stopped for a certain period of time (paddle method), A method of spraying a developer on the surface (spray method) and a method of continuously discharging a developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispense method), and the like. No.

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

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

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

Examples of a method for removing impurities such as metals from the above various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore sizes and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step. As the filter, a filter having a reduced amount of eluted material as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Application Laid-Open No. 2006-201426) is preferable.
In addition to filter filtration, removal of impurities by an adsorbent may be performed, or filter filtration and an adsorbent may be used in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (JP-A-2006-206500).
In addition, as a method of reducing impurities such as metals contained in the various materials, a material having a low metal content is selected as a material constituting the various materials, and a filter filtration is performed on the materials constituting the various materials. Alternatively, there is a method in which distillation is performed under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark). Preferred conditions for filter filtration performed on raw materials constituting various materials are the same as those described above.

  The above-mentioned various materials are described in U.S. Patent Application Publication No. 2015/0227049 and Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Laid-Open No. 2015-123351) in order to prevent contamination of impurities. It is preferable to store it in a sealed container.

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

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

  Hereinafter, the present invention will be described in more detail based on examples. Materials, used amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

Hereinafter, various components contained in the actinic ray-sensitive or radiation-sensitive resin composition shown in Table 1 are shown.
<Resin>
The structures of the resins (resins P-1 to P-6) shown in Table 1 are shown below.
The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of the resins P-1 to P-6 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). The composition ratio (molar% ratio) of the resin was measured by ¹³ C-NMR (nuclear magnetic resonance).

<Acid generator>
The structures of the acid generators (PAG-1 to PAG-12) shown in Table 1 are shown below.
Note that PAG-1 to PAG-5, PAG-7, and PAG-8 correspond to the compound represented by the general formula (ZI-3). PAG-6 corresponds to the compound represented by the general formula (ZI-4).

<Acid diffusion controller>
The structures of the acid diffusion controllers (D-1 to D-4) shown in Table 1 are shown below.

<Crosslinking agent>
The structures of the crosslinking agents (A-1 to A-8) shown in Table 1 are shown below.

<Surfactant>
The surfactants shown in Table 1 are shown below.
W-1: PF6320 (manufactured by OMNOVA Corporation)
W-2: Megafac F176 (manufactured by DIC Corporation; fluorine type)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)

<Solvent>
The solvents shown in Table 1 are shown below.
SL-1: Propylene glycol monomethyl ether (1-methoxy-2-propanol)
SL-2: Propylene glycol monomethyl ether acetate (1-methoxy-2-acetoxypropane)
SL-3: 2-heptanone SL-4: cyclohexanone SL-5: γ-butyrolactone SL-6: propylene carbonate

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in Table 1 were mixed and adjusted for the solid content so that the film thickness after pattern formation was 11 μm. Then, the obtained mixed solution is filtered in the order of a polyethylene filter having a pore size of 50 nm, a nylon filter having a pore size of 10 nm, and finally a polyethylene filter having a pore size of 5 nm to obtain actinic ray-sensitive or radiation-sensitive. A liquid resin composition (hereinafter, also referred to as a resin composition) was prepared. In the resin composition, the solid content means all components other than the solvent. The obtained resin compositions were used in Examples and Comparative Examples.
In addition, 25 kinds (Na, K, Ca, Fe, Cu, Mg, Mn, Al, Li, Cr, Ni, Sn, Zn, Ag, As, Au, Ba, Cd, Co, Pb contained in each composition) , Ti, V, W, Mo, Zr) were measured with an ICP-MS device (Inductively Coupled Plasma Mass Spectrometer) “Agilent 7500cs” manufactured by Agilent Technologies, and the content of each metal species was as follows. Each was less than 10 ppb.

[Pattern formation and various evaluations]
<Negative pattern formation: KrF exposure, alkali development>
Using a spin coater ACT-8 manufactured by Tokyo Electron, the prepared resist composition was stopped without providing an antireflection layer on a Si substrate (manufactured by Advanced Materials Technology) subjected to hexamethyldisilazane treatment. It dripped in the state. After dropping, the substrate is rotated, and the number of rotations is maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, further maintained at 500 rpm for 3 seconds, and again at 100 rpm for 2 seconds, and then the film thickness is set. The number was increased to 1200 rpm and maintained for 60 seconds. Thereafter, drying was performed by heating at 130 ° C. for 60 seconds on a hot plate to form a resist film having a thickness of 11 μm. This resist film was exposed using a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C wavelength: 248 nm). After the irradiation, the substrate was baked at 110 ° C. for 90 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with pure water for 30 seconds and dried.

<Performance evaluation>
The obtained pattern was evaluated by the following method.
(Resolution limit CD (Critical Dimension) (nm))
Observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), the space width at the substrate interface in the cross section of the non-resist part (line / space = 4: 1) in the formed resist pattern was determined. It was set as the resolution limit CD and evaluated.
The results are shown in Table 2.

(aspect ratio)
The aspect ratio was determined by the following equation (1).
Formula (1): film thickness after pattern formation (11 μm) / obtained resolution limit CD (nm)
The results are shown in Table 2.

(Shape evaluation)
From the results of the cross-sectional SEM (Scanning Electron Microscope) of the wafer after development, it was possible to resolve the pattern up to the substrate. A sample having poor linearity (a projecting bottom portion) was evaluated as B.
The results are shown in Table 2.

When the actinic ray-sensitive or radiation-sensitive resin compositions of Examples 1 to 10 were used, it was confirmed that resolution and shape characteristics were excellent.
From the comparison of Examples 1 to 10, when a resin containing a repeating unit (a1) containing a phenolic hydroxyl group and a repeating unit represented by the general formula (3) is used (corresponding to resin P-1) , Resolution and shape characteristics were confirmed to be more excellent.
On the other hand, when the actinic ray-sensitive or radiation-sensitive resin compositions of Comparative Examples 1 to 4 were used, it was confirmed that the desired effects could not be obtained in both resolution and shape characteristics.

Claims (12)

A negative actinic ray-sensitive or radiation-sensitive resin composition having a film thickness of 1 μm or more,
At least one acid generator selected from the group consisting of a compound represented by the following general formula (ZI-3) and a compound represented by the following general formula (ZI-4),
A crosslinking agent,
At least one selected from the group consisting of a repeating unit containing a reactive group capable of reacting with the crosslinking agent, and a repeating unit containing a structure protected by a leaving group which is decomposed and eliminated by the action of an acid; An actinic ray-sensitive or radiation-sensitive resin composition comprising: a resin having a kind of repeating unit.

In Formula (ZI-3), R _{1c to} R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, Represents an alkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group.
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
Note that any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y are each independently bonded to each other to form a ring. May be formed, and the ring may include an oxygen atom, a sulfur atom, a carbonyl group, an ester bond, or an amide bond.
Zc ^- represents an anion.

In Formula (ZI-4), R ₁₃ represents a group including a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group.
R ₁₄ represents a group containing a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group, when a plurality of groups are present, Represents
R ₁₅ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group.
In addition, two R ₁₅ may be bonded to each other to form a ring, and the ring may include a hetero atom.
l represents an integer of 0 to 2.
r represents an integer of 0 to 8.
Z ^- represents an anion.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, which is used for forming a pattern having a thickness of 1 to 100 µm.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, which forms a pattern by being exposed to light having an absorption wavelength of 248 nm or more.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the resin is an alkali-soluble resin.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the resin contains a phenolic hydroxyl group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the resin contains a repeating unit represented by the following general formula (I).

In the formula (I), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₄₂ may combine with Ar ₄ to form a ring, in which case R ₄₂ represents a single bond or an alkylene group.
X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or a divalent linking group.
Ar ₄ represents an (n + 1) -valent aromatic hydrocarbon group, and represents an (n + 2) -valent aromatic hydrocarbon group when bonded to R ₄₂ to form a ring.
n represents an integer of 1 to 5. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein the resin further contains a repeating unit represented by the following general formula (3).

In the general formula (3), R ₂₃ represents a hydrogen atom or an alkyl group.
X _A represents a group containing a polycyclic alicyclic structure of non-acid-decomposable.
Ar ₁ represents a (m + 1) -valent aromatic ring group.
m is an integer of 1 or more.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein the crosslinking agent is a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in a molecule.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8, wherein the crosslinking agent comprises two or more compounds containing two or more alkoxymethyl groups in a molecule.   A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1. A resist film forming step of forming a resist film having a thickness of 1 μm or more using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9,
An exposure step of exposing the resist film,
A developing step of developing the exposed resist film using a developing solution. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 11.