WO2020049863A1

WO2020049863A1 - Actinic ray-sensitive or radiation-sensitive resin composition, pattern forming method, resist film, and method for producing electronic device

Info

Publication number: WO2020049863A1
Application number: PCT/JP2019/027224
Authority: WO
Inventors: 敬充冨賀; 英明椿; 東　耕平; 康智米久田; 直也畠山
Original assignee: 富士フイルム株式会社
Priority date: 2018-09-05
Filing date: 2019-07-09
Publication date: 2020-03-12
Also published as: JP7096892B2; JPWO2020049863A1; TW202010763A

Abstract

Provided is an actinic ray-sensitive or radiation-sensitive resin composition which contains : a resin (A); a solvent (B); and a photoacid generator, wherein the resin (A) includes a non-acid-decomposable repeating unit (a1) derived from a monomer having a glass transition temperature of 50°C or less when formed into a homopolymer, and a repeating unit (a2) having an acid-decomposable group, and also includes a repeating unit having an aromatic ring, and the solvent (B) has a boiling point of 135°C or less, and a viscosity of 1.5 mPa or less. Also provided are a resist film using the composition, a pattern forming method, and a method for producing an electronic device.

Description

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

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, a resist film, 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) to convert an alkali-insoluble group into an alkali-soluble group using the generated acid as a reaction catalyst, and remove an exposed portion with an alkali developing solution.

On the other hand, in recent years, miniaturization using the wavelength of an exposure light source is approaching its limit. In particular, in an application process for an implantation process and a NAND memory (NOT AND memory), a three-dimensional memory layer is required to increase the capacity. It is becoming mainstream. 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.

For example, Patent Literature 1 describes a resist composition containing a specific resin, a specific organic solvent, and an acid generator.

JP 20162066673 A

However, when an object to be etched is etched using a thick film pattern formed by lithography from the resist composition described in Patent Literature 1 as a mask, cracks (cracks) may occur in the mask formed of the pattern. Do you get it. In addition, voids (voids) were found inside the pattern.

Further, after applying a resist composition described in Patent Document 1 on a substrate and drying a thick resist film obtained for a certain period of time, pattern exposure and development were performed. It has been found that a CD (Critical Dimension) variation such as a failure to obtain a width pattern occurs. That is, it was found that the resist composition described in Patent Document 1 was inferior in PCD (Post Coating Delay) performance.

Therefore, the present invention provides an actinic ray-sensitive or radiation-sensitive resin which is excellent in PCD performance and is capable of forming a pattern in which cracks are hardly generated in etching and in which voids are hardly generated inside the pattern. It is an object to provide a composition, a resist film using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device.

The present inventors have conducted intensive studies to solve the above-described problems, and according to the active light-sensitive or radiation-sensitive resin composition containing a resin having a specific structure and a solvent having a specific boiling point and a specific viscosity. The present inventors have found that the above-mentioned problems can be solved, and completed the present invention.

That is, the present inventors have found that the above configuration can achieve the above object.

[1]

An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A), a solvent (B), and a compound that generates an acid upon irradiation with actinic rays or radiation,

The resin (A) includes a repeating unit (a1) derived from a monomer having a glass transition temperature of 50 ° C. or lower when formed into a homopolymer, and a repeating unit (a2) having an acid-decomposable group,

The repeating unit (a1) is a non-acid-decomposable repeating unit,

The resin (A) has a repeating unit having an aromatic ring,

The solvent (B) has a boiling point of 135 ° C. or less and a viscosity of 1.5 mPa · s or less,

An actinic ray-sensitive or radiation-sensitive resin composition used for forming a film having a thickness of 1 to 30 μm.

[2]

The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit (a1) is a repeating unit represented by the following general formula (1-2).

In the general formula (1-2), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₂ represents a non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a hetero atom in the chain.

[3]

The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit (a1) is a repeating unit represented by the following general formula (1-3).

In the general formula (1-3), R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₄ may be a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group which may contain a hetero atom in the chain, or a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group which may contain a hetero atom in the ring member. Represents an acid-decomposable cycloalkyl group.

[4]

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the viscosity of the solvent (B) is 1.2 mPa · s or less.

[5]

The actinic ray-sensitive or radiation-sensitive radiation according to any one of [1] to [4], wherein the solvent (B) is at least one selected from an aromatic solvent, a ketone solvent, and an ester solvent. Resin composition.

[6]

The solvent according to any one of [1] to [5], wherein the solvent (B) is at least one selected from methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, ethyl acetate, isobutyl acetate, and butyl acetate. Actinic ray- or radiation-sensitive resin composition.

[7]

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the solvent (B) is at least one selected from methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone. object.

[8]

The photosensitive composition according to any one of [1] to [7], wherein the content of the solvent (B) is 20% by mass or more based on the total amount of the solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition. Actinic ray- or radiation-sensitive resin composition.

[9]

(I) a step of forming an actinic ray-sensitive or radiation-sensitive film having a thickness of 1 to 30 μm on a substrate with the actinic ray-sensitive or radiation-sensitive resin composition;

(Ii) irradiating the actinic ray-sensitive or radiation-sensitive film with actinic ray or radiation, and

(Iii) developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation using a developer.

A pattern forming method, wherein the actinic ray-sensitive or radiation-sensitive resin composition is the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].

[10]

A resist film having a film thickness of 1 to 30 μm, formed by the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].

[11]

A method for manufacturing an electronic device, including the pattern forming method according to [9].

According to the present invention, an actinic ray-sensitive or radiation-sensitive resin which is excellent in PCD performance, hardly generates cracks in a pattern during etching, and can form a pattern in which voids are hardly generated inside the pattern A composition, a resist film using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device can be provided.

Hereinafter, the present invention will be described in detail.

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

As used herein, the term “actinic ray” or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet represented by excimer laser, extreme ultraviolet (EUV: Extreme Ultraviolet), X-ray, soft X-ray, and electron. It means a line (EB: Electron Beam) or the like. As used herein, “light” means actinic rays or radiation. Unless otherwise specified, the term "exposure" in the present specification means not only exposure with a bright line spectrum of a mercury lamp, far ultraviolet represented by excimer laser, extreme ultraviolet, X-ray, and EUV, but also electron beam and ion. Drawing by particle beams such as beams is also included.

In the present 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 the present specification, (meth) acrylate represents at least one of acrylate and methacrylate. (Meth) acrylic acid represents at least one of acrylic acid and methacrylic acid.

In this 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 determined by a GPC (Gel Permeation Chromatography) apparatus (HLC manufactured by Tosoh Corporation). GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: It is defined as a polystyrene-equivalent value obtained by a differential 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.

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

(Substituent T)

Examples of the substituent T include 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; and 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 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; Kill 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; An amino group; an arylamino group; 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”) comprises a resin (A), a solvent (B), and an acid or a radiation. An actinic ray-sensitive or radiation-sensitive resin composition containing a compound generating

The resin (A) includes a repeating unit (a1) derived from a monomer having a glass transition temperature of 50 ° C. or lower when formed into a homopolymer, and a repeating unit (a2) having an acid-decomposable group,

The repeating unit (a1) is a non-acid-decomposable repeating unit,

The resin (A) has a repeating unit having an aromatic ring,

The solvent (B) has a boiling point of 135 ° C. or less and a viscosity of 1.5 mPa · s or less,

An actinic ray-sensitive or radiation-sensitive resin composition used for forming a film having a thickness of 1 to 30 μm.

The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Further, the resist composition may be a resist composition for alkali development or a resist composition for organic solvent development. Among them, a positive resist composition, and preferably a resist composition for alkali development.

The composition of the present invention is typically a chemically amplified resist composition.

The reason why the composition of the present invention can form a pattern which is excellent in PCD performance, hardly generates cracks in the pattern during etching, and hardly generates voids in the pattern is clearly explained in detail. Although it is not, it is estimated as follows.

It is considered that the problem of the PCD performance of the conventional resist composition is caused by the fact that the solvent remaining in the resist film formed using the resist composition volatilizes when left. Further, it is considered that cracks and voids generated in the pattern at the time of etching are also caused by the solvent remaining in the pattern. That is, a solvent is left in a pattern (resist pattern) obtained by forming a resist film using a conventional resist composition, and exposing and developing, and is used in a CD-evaluated SEM (Scanning Electron Microscope). In a process such as evacuation performed when a wafer is inserted into the substrate, or in a process such as evacuation performed when etching the object to be etched using the pattern as a mask (typically, plasma etching), it remains inside the pattern. It is considered that the solvent is volatilized, stress is generated in the pattern, cracks are generated, and voids are generated.

In the present invention, a homopolymer is used as an acid-decomposable resin in order to use a solvent having a low boiling point (solvent (B)) which is easy to volatilize, and to make the resist film and the resist pattern flexible and to easily volatilize the remaining solvent. The above problem could be solved by using a resin (resin (A)) having a repeating unit (repeating unit (a1)) derived from a monomer having a glass transition temperature of 50 ° C. or lower. It is considered something.

Further, in the present invention, by using a low-viscosity solvent (solvent (B)), the solvent volatilization at the time of coating can be promoted, the solvent remaining in the film can be reduced, and the above problem can be solved. It is considered possible.

<Resin (A)>

The resin (A) contained in the composition of the present invention has a repeating unit (a1) derived from a monomer having a glass transition temperature (Tg) of 50 ° C. or lower when formed into a homopolymer, and an acid-decomposable group. And the repeating unit (a1) is a non-acid-decomposable repeating unit. Further, the resin (A) has a repeating unit having an aromatic ring.

Since the resin (A) contains a repeating unit having an acid-decomposable group, it is a resin (acid-decomposable resin) which is decomposed by the action of an acid to increase polarity. That is, in the pattern forming method of the present invention described later, typically, when an alkali developing solution is used as a developing solution, a positive pattern is suitably formed, and when an organic developing solution is used as a developing solution. , A negative pattern is suitably formed.

(Repeating unit (a1))

The repeating unit (a1) is a repeating unit derived from a monomer having a glass transition temperature of 50 ° C. or lower when formed into a homopolymer (also referred to as “monomer a1”).

The repeating unit (a1) is a non-acid-decomposable repeating unit. Therefore, the repeating unit (a1) does not have an acid-decomposable group.

(Method of measuring glass transition temperature of homopolymer)

If there is a catalog value or literature value, the glass transition temperature of the homopolymer is taken. If not, the glass transition temperature is measured by a differential scanning calorimetry (DSC: Differential scanning calorimetry) method. The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg is 18,000, and the degree of dispersion (Mw / Mn) is 1.7. As the DSC device, a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Co., Ltd. is used, and the temperature is measured at a rate of 10 ° C./min.

The homopolymer used for the measurement of Tg may be synthesized by a known method using the corresponding monomer, and can be synthesized by, for example, a general drop polymerization method. An example is shown below.

54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was heated to 80 ° C. under a nitrogen stream. While stirring this solution, 125 parts by mass of a PGMEA solution containing 21% by mass of the corresponding monomer and 0.35% by mass of dimethyl 2,2′-azobisisobutyrate were added dropwise over 6 hours. After the completion of the dropwise addition, the mixture was further stirred at 80 ° C. for 2 hours. After allowing the reaction solution to cool, it is reprecipitated with a large amount of methanol / water (mass ratio 9: 1), filtered, and the obtained solid is dried to obtain a homopolymer (Mw: 18000, Mw / Mn: 1.7). I got The obtained homopolymer was subjected to DSC measurement. The DSC apparatus and the heating rate were as described above.

The monomer a1 is not particularly limited as long as it has a glass transition temperature (Tg) of 50 ° C. or lower when formed into a homopolymer. From the viewpoints of improving PCD performance, suppressing crack generation, and reducing voids in the pattern, homopolymers are used. It is preferable that Tg at that time is 30 ° C. or lower. The lower limit of Tg when the monomer a1 is a homopolymer is not particularly limited, and is often −80 ° C. or higher, preferably −70 ° C. or higher, more preferably −60 ° C. or higher, and still more preferably −80 ° C. or higher. 50 ° C. or higher.

The repeating unit (a1) is a repeating unit having a non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a hetero atom in the chain because the residual solvent can be more easily volatilized. Is preferred. In the present specification, "non-acid-decomposable" means that the acid generated by the photoacid generator does not cause the elimination / decomposition reaction.

That is, the “non-acid-decomposable alkyl group” more specifically refers to an alkyl group that does not leave the resin (A) due to the action of the acid generated by the photoacid generator, or a photoacid generator. Examples include an alkyl group that is not decomposed by the action of an acid.

The non-acid-decomposable alkyl group may be linear or branched.

Hereinafter, a repeating unit having a non-acid-decomposable alkyl group having 2 or more carbon atoms, which may include a hetero atom in the chain, will be described.

The non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a hetero atom in the chain, is not particularly limited. For example, an alkyl group having 2 to 20 carbon atoms, Examples thereof include an alkyl group having 2 to 20 carbon atoms and containing an atom.

Examples of the alkyl group having 2 to 20 carbon atoms containing a hetero atom in the chain include one or two or more —CH ₂ — of —O—, —S—, —CO—, —NR ₆ — Or an alkyl group substituted with a divalent organic group obtained by combining two or more of these. R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The non-acid-decomposable alkyl group having 2 or more carbon atoms that may contain a hetero atom in the chain includes, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Heptyl, octyl, nonyl, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethylpentyl, and 2-ethylhexyl, and one or more of these And a monovalent alkyl group in which CH ₂ — is substituted with —O— or —O—CO—.

The carbon number of the non-acid-decomposable alkyl group which may contain a hetero atom in the chain and has 2 or more carbon atoms is preferably 2 or more and 16 or less, more preferably 2 or more and 10 or less. More preferably, it is 2 or more and 8 or less.

The non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (for example, substituent T).

The repeating unit (a1) is preferably a repeating unit represented by the following general formula (1-2).

In the general formula (1-2), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₂ represents a non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a hetero atom in the chain.

The halogen atom represented by R ₁ is not particularly limited, but includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The alkyl group represented by R ₁ is not particularly limited, but includes, for example, an alkyl group having 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, and a tert-butyl group. . Among them, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.

The cycloalkyl group represented by R ₁ is not particularly limited, but includes, for example, a cycloalkyl group having 5 to 10 carbon atoms, and more specifically, a cyclohexyl group.

The R _1, preferably a hydrogen atom or a methyl group is preferable.

The definition and preferred embodiments of the non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a hetero atom in the chain represented by R ₂ are as described above.

In addition, the repeating unit (a1) is a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the chain, or a ring member because the residual solvent can be more easily volatilized. It may be a repeating unit having a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group which may contain a hetero atom.

Hereinafter, a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the chain, or a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in a ring member. The repeating unit having a functional cycloalkyl group will be described.

The non-acid-decomposable alkyl group may be linear or branched.

The carbon number of the non-acid-decomposable alkyl group is preferably 2 or more, and from the viewpoint that the Tg of the homopolymer is 50 ° C or lower, the upper limit of the carbon number of the non-acid-decomposable alkyl group is, for example, 20 or less. preferable.

The non-acid-decomposable alkyl group which may contain a hetero atom in the chain is not particularly limited, and examples thereof include an alkyl group having 2 to 20 carbon atoms and a carbon number having a hetero atom in the chain. And 2 to 20 alkyl groups. In addition, at least one of the hydrogen atoms in the alkyl group is substituted with a carboxy group or a hydroxyl group.

Examples of the alkyl group having 2 to 20 carbon atoms containing a hetero atom in the chain include one or two or more —CH ₂ — of —O—, —S—, —CO—, —NR ₆ — Or an alkyl group substituted with a divalent organic group obtained by combining two or more of these. R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The carbon number of the non-acid-decomposable alkyl group which may contain a hetero atom in the chain is preferably from 2 to 16, and more preferably from 2 to 10, from the viewpoint of being more excellent in crack resistance (hard to generate cracks). Preferably, 2 to 8 are more preferable.

The non-acid-decomposable alkyl group may have a substituent (for example, substituent T).

Specific examples of the repeating unit having a non-acid-decomposable alkyl group having a carboxy group and containing a hetero atom in the chain include a repeating unit having the following structure.

The carbon number of the non-acid-decomposable cycloalkyl group is preferably 5 or more, and from the viewpoint that the Tg of the homopolymer is 50 ° C or less, the upper limit of the carbon number of the non-acid-decomposable cycloalkyl group is, for example, 20 or less. Is preferably, and more preferably 16 or less, and further preferably 10 or less.

The non-acid-decomposable cycloalkyl group which may contain a hetero atom in the ring member is not particularly limited, and includes, for example, a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group), and And a cycloalkyl group having 5 to 20 carbon atoms containing a heteroatom in the ring member. In addition, at least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxy group or a hydroxyl group.

Examples of the C 5-20 cycloalkyl group containing a heteroatom as a ring member include one or more of —CH ₂ — in which —O—, —S—, —CO—, and —NR ₆ Or a cycloalkyl group substituted with a divalent organic group obtained by combining two or more of these. R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The non-acid-decomposable cycloalkyl group may have a substituent (for example, substituent T).

A non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group which may contain a hetero atom in the chain, or a non-acid-decomposable cyclo group having a carboxy group or a hydroxyl group which may contain a hetero atom in a ring member. As the repeating unit having an alkyl group, a repeating unit represented by the following general formula (1-3) is particularly preferable in terms of being more excellent in the effects of the present invention.

In the general formula (1-3), R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₄ may be a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group which may contain a hetero atom in the chain, or a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group which may contain a hetero atom in the ring member. Represents an acid-decomposable cycloalkyl group.

In formula (1-3), R ₃ has the same meaning as R ₁ described above, and the preferred embodiments are also the same.

A non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group which may contain a hetero atom in the chain represented by R ₄ , or a carboxy group or a hydroxyl group which may contain a hetero atom in the ring member. The definition and the preferable embodiment of the non-acid-decomposable cycloalkyl group are as described above.

Among them, R ₄ is preferably a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the ring member.

Examples of the monomer a1 include ethyl acrylate (−22 ° C.), n-propyl acrylate (−37 ° C.), isopropyl acrylate (−5 ° C.), n-butyl acrylate (−55 ° C.), and n-butyl methacrylate (20 ° C.). ), N-hexyl acrylate (−57 ° C.), n-hexyl methacrylate (−5 ° C.), n-octyl methacrylate (−20 ° C.), 2-ethylhexyl acrylate (−70 ° C.), isononyl acrylate (− 82 ° C), lauryl methacrylate (-65 ° C), 2-hydroxyethyl acrylate (-15 ° C), 2-hydroxypropyl methacrylate (26 ° C), 1- [2- (methacryloyloxy) ethyl] succinate (9 ° C) , 2-ethylhexyl methacrylate (-10 ° C), sec-butyl acrylate -26 ° C.), methoxy polyethylene glycol monomethacrylate (n = 2) (- 20 ℃), hexadecyl acrylate (35 ℃), 4- hydroxycyclohexyl acrylate (15 ° C.), and the like. The values in parentheses indicate Tg (° C.) of the homopolymer.

Note that methoxypolyethylene glycol monomethacrylate (n = 2) is a compound having the following structure.

The monomer a1 is preferably n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, 4-hydroxycyclohexyl acrylate or lauryl methacrylate.

The resin (A) may include only one type of the repeating unit (a1), or may include two or more types of the repeating unit (a1).

In the resin (A), the content of the repeating unit (a1) (when there are a plurality of repeating units (a1), the total thereof) is preferably at least 5 mol% based on all the repeating units of the resin (A). 10 mol% or more is more preferable, 50 mol% or less is preferable, 40 mol% or less is more preferable, and 30 mol% or less is still more preferable. In particular, the content of the repeating unit (a1) in the resin (A) (when there are a plurality of repeating units (a1), the total content thereof) is 5 to 50 mol% based on all the repeating units of the resin (A). Is preferably 5 to 40 mol%, more preferably 5 to 30 mol%.

(Repeating unit (a2))

The resin (A) has a repeating unit (a2) having an acid-decomposable group.

The resin (A) may have one kind of the repeating unit (a2) having an acid-decomposable group, or may have two or more kinds thereof.

In the resin (A), the content of the repeating unit (a2) (when there are a plurality of repeating units (a2), the sum thereof) may be 20 mol% or less based on all the repeating units of the resin (A). It is more preferably 15 mol% or less in terms of PCD performance, crack resistance, suppression of voids inside the pattern and etching resistance. In addition, the lower limit of the content of the repeating unit (a2) is, for example, 3 mol% or more, and preferably 5 mol% or more, based on all the repeating units of the resin (A).

The acid-decomposable group preferably has a structure in which a polar group is protected by a group capable of decomposing and leaving by the action of an acid (leaving group).

Examples of the polar group include a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfo group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkylcarbonyl) imide Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) methylene group And the like (a group that dissociates in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), and an alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring. Aliphatic alcohols substituted with a functional group (eg, hexafluoroisopropanol group) are excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

Preferred polar groups include a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfo group.

Preferred groups as the acid-decomposable group are groups in which a hydrogen atom of these groups is substituted with a group capable of leaving by the action of an acid (leaving group).

Examples of the group leaving by the action of an acid (leaving group) include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and- C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and the like.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may combine with each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl And octyl groups.

Cycloalkyl group _{_R} ₃₆ ~ R _39, R ₀₁ and _{R 02} may be monocyclic or polycyclic.

As the monocyclic cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, for example, an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, Examples include a tetracyclododecyl group and an androstanyl group. In addition, at least one carbon atom in the cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.

The aryl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

The aralkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, for example, a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group and the like.

The ring formed by bonding R ₃₆ and R ₃₇ to each other is preferably a cycloalkyl group (monocyclic or polycyclic). As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable. .

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group, and more preferably an acetal group or a tertiary alkyl ester group.

.Repeating units having a structure (acid-decomposable group) protected by a leaving group in which a -COO- group is decomposed and eliminated by the action of an acid

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

In the general formula (AI),

Xa ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group.

T represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group.

Any two of Rx ₁ to Rx ₃ may or may not form a ring structure.

Examples of the divalent linking group for T include an alkylene group, an arylene group, -COO-Rt-, -O-Rt-, and the like. In the formula, Rt represents an alkylene group, a cycloalkylene group or an arylene group.

T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and more preferably —CH ₂ —, — (CH ₂ ) ₂ —, or — (CH ₂ ) ₃ —. T is more preferably a single bond.

Xa ₁ is preferably a hydrogen atom or an alkyl group.

The alkyl group of Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably, a fluorine atom).

The alkyl group of Xa ₁ preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group. The alkyl group for Xa ₁ is preferably a methyl group.

The alkyl group for Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, An isobutyl group or a t-butyl group is preferred. The carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. In the alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ , some of the carbon-carbon bonds may be double bonds.

Examples of the cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group Are preferred.

Examples of the ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ include a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, a norbornane ring, and a tetracyclo ring. Polycyclic cycloalkyl rings such as a decane ring, a tetracyclododecane ring, and an adamantane ring are preferred. Among them, a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferred. As the ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ , the following structures are also preferable.

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

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

The resin (A) is decomposed by the action of an acid described in paragraphs <0363> to <0364> of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having an acid-decomposable group to form an alcoholic resin. It may have a repeating unit containing a group generating a hydroxyl group.

.Repeating unit having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed and eliminated by the action of an acid

The resin (A) preferably has, as a repeating unit having an acid-decomposable group, a repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group which is decomposed and eliminated by the action of an acid. 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.

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 alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups.

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 for 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 for 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 to R ₃₈ each independently represent a hydrogen atom or 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 more preferably an aryl group.

As the repeating unit having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed and eliminated by the action of an acid, a hydrogen atom in the phenolic hydroxyl group is represented by any of formulas (Y1) to (Y4) Those having a structure protected by a group represented by

As the repeating unit having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed and eliminated by the action of an acid, 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, in which 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 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.

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

(Other repeating units)

The resin (A) may contain other repeating units in addition to the above-mentioned repeating units.

Hereinafter, other repeating units that may be contained in the resin (A) will be described in detail.

(Repeating unit having carboxyl group (a3))

The resin (A) may have a repeating unit (a3) having a carboxy group in addition to the repeating unit (a1) and the repeating unit (a2).

Since the resin (A) contains the repeating unit (a3), the resin (A) is more excellent in dissolution rate during alkali development.

Examples of the repeating unit (a3) include the following repeating units derived from (meth) acrylic acid.

The resin (A) may have one type of the repeating unit (a3) alone, or may have two or more types of the repeating unit (a3) in combination.

In the resin (A), the content of the repeating unit (a3) is preferably from 1 to 10 mol%, more preferably from 2 to 8 mol%, based on all repeating units in the resin (A).

(Repeating unit (a4) having a phenolic hydroxyl group)

The resin (A) may further have a repeating unit (a4) having a phenolic hydroxyl group in addition to the repeating unit (a1) and the repeating unit (a2).

Since the resin (A) contains the repeating unit (a4), the resin (A) is excellent in dissolution rate during alkali development and excellent in etching resistance.

The repeating unit having a phenolic hydroxyl group is not particularly limited, but includes a hydroxystyrene repeating unit or a hydroxystyrene (meth) acrylate repeating unit. As the repeating unit having a phenolic hydroxyl group, a repeating unit represented by the following general formula (I) is preferable.

Where:

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. An alkyl group having 20 or less carbon atoms such as a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and 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, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, and an acyl group. 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. When n is 1, the divalent aromatic hydrocarbon group 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. Preferred are groups or aromatic hydrocarbon groups containing heterocycles such as, for example, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

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 A group obtained by removing a hydrogen atom can be 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;

_-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 Alkyl groups having 20 or less carbon atoms, such as isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, are preferred, and alkyl groups having 8 or less carbon atoms are more preferred. .

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

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

Ar ₄ is preferably an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group. 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.

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

The resin (A) may have one type of the repeating unit (a4) alone, or may have two or more types of the repeating unit (a4) in combination.

In the resin (A), the content of the repeating unit (a4) is preferably at least 40 mol%, more preferably at least 50 mol%, and even more preferably at least 60 mol%, based on all repeating units in the resin (A). preferable. Further, the content of the repeating unit (a4) is preferably at most 85 mol%, more preferably at most 80 mol%, based on all repeating units in the resin (A).

(Repeating unit (a5))

The resin (A) may have a repeating unit (a5) having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

The lactone structure or sultone structure may have a lactone structure or a sultone structure, and is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure. Among them, a 5- to 7-membered lactone structure in which a bicyclo structure or a spiro structure is formed and another ring structure is condensed, or a 5- to 7-membered ring in which a bicyclo structure or a spiro structure is formed is formed. Those in which another ring structure is fused to the sultone structure are more preferred.

The resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or any one of the following general formulas (SL1-1) to (SL1-3) It is more preferred to have a repeating unit having a sultone structure represented. Further, a lactone structure or a sultone structure may be directly bonded to the main chain. As a preferable structure, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1-16) A lactone structure represented by -21) or a sultone structure represented by the general formula (SL1-1).

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

As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III) is preferable.

In the above general formula (III),

A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).

n is the number of repetitions of the structure represented by —R ₀ —Z—, represents an integer of 0 to 5, is preferably 0 or 1, and is more preferably 0. When n is 0, -R ₀ -Z- does not exist and becomes a single bond.

R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. If R ₀ is plural, R ₀ each independently represents a alkylene group, a cycloalkylene group, or a combination thereof.

Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are two or more Zs, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.

R ₇ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

The alkylene group or cycloalkylene group of R ₀ may have a substituent.

As Z, an ether bond or an ester bond is preferable, and an ester bond is more preferable.

The resin (A) may have a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.

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

In the general formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

n represents an integer of 0 or more.

R _A ² represents a substituent. when n is 2 or _{more, R} ^{A 2} each independently represent a substituent.

A represents a single bond or a divalent linking group.

Z represents an atomic group forming a monocyclic structure or a polycyclic structure together with the group represented by -OC (= O) -O- in the formula.

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

The resin (A) may have one kind of a repeating unit having at least one kind selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may have two or more kinds in combination. May be.

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

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

The content of a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure contained in the resin (A) (selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure) When there are a plurality of repeating units having at least one kind, the total is preferably 5 to 30 mol%, more preferably 10 to 30 mol%, and more preferably 20 to 30 mol%, based on all the repeating units in the resin (A). 30 mol% is more preferred.

The resin (A) may have, in addition to the above-mentioned repeating structural units, dry etching resistance, suitability for a standard developer, substrate adhesion, a resist profile, or resolution, heat resistance, sensitivity and the like, which are general necessary properties of a resist. May have various repeating structural units for the purpose of adjusting.

Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a predetermined monomer.

The predetermined monomer has, for example, one addition-polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. And the like.

In addition, an addition-polymerizable unsaturated compound copolymerizable with a monomer corresponding to the above-mentioned various repeating structural units may be used.

In the resin (A), the molar ratio of each repeating structural unit is appropriately set to adjust various performances.

In the resin (A), it is preferable that all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, any of those in which all of the repeating units are methacrylate-based repeating units, those in which all of the repeating units are acrylate-based repeating units, and those in which all of the repeating units are composed of methacrylate-based repeating units and acrylate-based repeating units. Although it can be used, it is preferable that the acrylate-based repeating unit is 50 mol% or less based on all the repeating units of the resin (A).

(Repeating unit having aromatic ring)

The resin (A) has a repeating unit having an aromatic ring. The resin (A) may have only one type of repeating unit having an aromatic ring, or two or more types of repeating units.

In the resin (A), the content of the repeating unit having an aromatic ring is, for example, 40 mol% or more and 55 mol% with respect to all the repeating units in the resin (A) because the etching resistance is more excellent. Or more, more preferably 60 mol% or more. The upper limit is not particularly limited, but is, for example, 97 mol% or less, preferably 85 mol% or less, and more preferably 80 mol% or less.

(Method of polymerizing resin (A))

The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). Examples of general synthesis methods include (1) a batch polymerization method in which a monomer type and an initiator are dissolved in a solvent and polymerization is performed by heating, and (2) a solution containing the monomer type and an initiator in 1 to A drop polymerization method in which the mixture is added dropwise to a heating solvent by dropping over 10 hours, and the like can be mentioned. Among them, the drop polymerization method (2) is preferable.

Examples of the reaction solvent during the polymerization include ethers such as tetrahydrofuran, 1,4-dioxane, and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; dimethylformamide; Solvents that dissolve the composition of the present invention, such as amides such as acetamide, and propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and cyclohexanone described below. As the reaction solvent in the polymerization, it is preferable to use the same solvent as the solvent used in the composition of the present invention. Thereby, generation of particles during storage can be suppressed.

The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen and argon.

In the polymerization reaction, it is desirable to use a commercially available radical initiator (for example, an azo-based initiator and a peroxide) as a polymerization initiator. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is more preferable. Examples of such azo-based initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2′-azobis (2-methylpropionate)

And the like.

As described above, a polymerization initiator may be optionally added to the polymerization reaction. The method of adding the polymerization initiator to the system is not particularly limited, and may be a mode in which the polymerization initiator is added all at once or a mode in which the polymerization initiator is divided and added in plural times. In the polymerization reaction, the solid content of the reaction solution is usually 5 to 60% by mass, preferably 10 to 50% by mass. The reaction temperature is usually 10 to 150 ° C, preferably 30 to 120 ° C, more preferably 60 to 100 ° C. After the completion of the reaction, the polymer is recovered by a method such as pouring into a solvent to recover the powder or solid content.

The weight average molecular weight of the resin (A) 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 further preferably from 1.1 to 2.0. preferable.

In the composition of the present invention, the resin (A) may be used alone or in combination of two or more.

In the composition of the present invention, the content of the resin (A) is generally often 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more based on the total solid content. , 80% by mass or more is more preferable. The upper limit is not particularly limited, but is preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less.

(Solid content concentration)

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably has a solid content concentration of 10% by mass or more. As a result, for example, it becomes easy to form a thick film pattern having a film thickness of 1 μm or more (preferably 10 μm or more). In addition, the solid content concentration intends the mass percentage of the mass of other resist components (components that can constitute a resist film) excluding the solvent with respect to the total mass of the composition of the present invention.

<Solvent (B)>

The composition of the present invention contains a solvent (B) having a boiling point of 135 ° C. or less and a viscosity of 1.5 mPa · s or less.

The solvent (B) is preferably an organic solvent.

The viscosity of the solvent (B) is the viscosity at 1 atm (101325 Pa) and 23 ° C. The viscosity is measured by a viscometer (RE-85L manufactured by Toki Sangyo Co., Ltd.).

The viscosity of the solvent (B) is not a value of a mixed solvent but a value of a single component solvent.

The composition of the present invention contains one or more solvents as the solvent (B).

The boiling point of the solvent (B) is preferably 130 ° C. or lower, more preferably 125 ° C. or lower, from the viewpoint of PCD performance, crack resistance, and void suppression. In addition, the boiling point of the solvent (B) is preferably 40 ° C. or higher, and more preferably 50 ° C. or higher, from the viewpoint of uniformity of the film thickness during coating.

The viscosity of the solvent (B) is preferably 1.2 mPa · s or less, more preferably 1.0 mPa · s or less, from the viewpoint of PCD performance, crack resistance, and void suppression. In addition, the viscosity of the solvent (B) is preferably 0.1 mPa · s or more, and more preferably 0.3 mPa · s or more, from the viewpoint of film thickness uniformity during coating.

The solvent (B) preferably has a boiling point of 135 ° C. or less and a viscosity of 1.2 mPa · s or less, more preferably a boiling point of 130 ° C. or less and a viscosity of 1.2 mPa · s or less. More preferably, the boiling point is 125 ° C. or less and the viscosity is 1.0 mPa · s or less.

The solvent (B) is preferably at least one selected from aromatic solvents, ketone solvents, and ester solvents, and includes toluene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, ethyl acetate, isobutyl acetate, and It is more preferably at least one selected from butyl acetate, even more preferably at least one selected from methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, ethyl acetate, isobutyl acetate, and butyl acetate, and methyl ethyl ketone, methyl Particularly preferred is at least one selected from isobutyl ketone and cyclopentanone.

Hereinafter, the boiling point and the viscosity are shown for specific examples of the solvent (B).

From the viewpoints of PCD performance, crack resistance, and void suppression, the content of the solvent (B) is preferably 20% by mass or more, more preferably 45% by mass or more based on the total amount of the solvent contained in the composition of the present invention. More preferably, it is still more preferably 70% by mass or more.

<Solvent (F)>

The composition of the present invention may contain a solvent other than the solvent (B). A solvent other than the solvent (B) is also called a solvent (F).

In the composition of the present invention, a known resist solvent can be appropriately used as the solvent (F). For example, paragraphs <0665> to <0670> of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs [0210] to <0235> of U.S. Patent Application Publication 2015 / 0004544A1, and U.S. Patent Application Publication 2016 / 0237190A1. Known solvents disclosed in paragraphs <0424> to <0426> of the specification and paragraphs <0357> to <0366> of US Patent Application Publication No. 2016 / 02744458A1 can be suitably used.

Solvents that can be used in 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 optionally having a ring, a cyclic lactone, or an alkyl acetate is preferable. Glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, and cyclohexanone are more preferable, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, cyclohexanone, or 2-heptanone is more preferable. 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.

The solvent (F) preferably contains propylene glycol monomethyl ether acetate, may be a single solvent of propylene glycol monomethyl ether acetate, or may be a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

When the composition of the present invention contains the solvent (F), the content of the solvent (F) is preferably 80% by mass or less, more preferably 55% by mass or less, based on the total amount of the solvent. , 30% by mass or less.

<Compound that generates an acid upon irradiation with actinic rays or radiation>

The composition of the present invention contains a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation.

As the photoacid generator, a compound that generates an organic acid upon irradiation with actinic rays or radiation is preferable. Examples include a sulfonium salt compound, an iodonium salt compound, a diazonium salt compound, a phosphonium salt compound, an imidosulfonate compound, an oxime sulfonate compound, a diazodisulfone compound, a disulfone compound, and an o-nitrobenzyl sulfonate compound.

As the photoacid generator, a known compound that generates an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs <0125> to <0319> of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs <0086> to <0094> of U.S. Patent Application Publication 2015 / 0004544A1, and U.S. Patent Application Publication 2016/2016. Known compounds disclosed in paragraphs <0323> to <0402> of JP-A No. 0237190A1 can be suitably used.

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

In the general formula (ZI),

R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.

Two of R ₂₀₁ to R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group) and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —.

Z ⁻ represents an anion (preferably a non-nucleophilic anion).

Preferred embodiments of the cation in the general formula (ZI) include a compound (ZI-1), a compound (ZI-2), and a compound represented by the general formula (ZI-3) (compound (ZI-3)) described later. And the corresponding group in the compound represented by the general formula (ZI-4) (compound (ZI-4)).

Note that the photoacid generator may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of _R 201 _{~ R 203} of the compound represented by formula (ZI), and at least one of _R 201 _{~ R 203} of another compound represented by formula (ZI), a single bond Alternatively, a compound having a structure bonded via a linking group may be used.

First, compound (ZI-1) will be described.

Compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or some of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an aryldicycloalkylsulfonium compound.

The aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary includes a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a C 3 to C 15 alkyl group. Are preferred, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ each independently represent an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, carbon atom). (Equation 6 to 14), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

Next, the compound (ZI-2) will be described.

Compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in formula (ZI) each independently represent an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, and preferably has 1 to 20 carbon atoms.

R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group. An alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

As the alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ , preferably, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (eg, a methyl group, an ethyl group, A propyl group, a butyl group, and a pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (eg, a cyclopentyl group, a cyclohexyl group, and a norbornyl group).

R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, the compound (ZI-3) will be described.

In the general formula (ZI-3), M represents an alkyl group, a cycloalkyl group, or an aryl group, and when having a ring structure, the ring structure includes an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon atom. It may contain at least one carbon double bond. 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 _6c and R _7c may combine to form a ring. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group. R _x and R _y may combine to form a ring. Further, at least two _members selected from M, R _6c and R _7c may combine to form a ring structure, and the ring structure may contain a carbon-carbon double bond. Z ⁻ represents an anion.

In the general formula (ZI-3), as the alkyl group and cycloalkyl group represented by M, a straight-chain alkyl group having 1 to 15 (preferably 1 to 10) carbon atoms and a C 3 to 15 ( Preferable is a branched alkyl group having 3 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Specifically, a methyl group, an ethyl group, a propyl group , N-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, norbornyl group and the like.

The aryl group represented by M is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.

M may further have a substituent (for example, substituent T). In this embodiment, for example, M is a benzyl group.

When M has a ring structure, the ring structure may include at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.

_Examples of the alkyl group, cycloalkyl group, and aryl group represented by R _6c and R _7c include those similar to M described above, and preferred embodiments thereof are also the same. Further, R _6c and R _7c may combine to form a ring.

Examples of the halogen atom represented by R _6c and R _7c include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group and the cycloalkyl group represented by R _x and R _y include those similar to M described above, and the preferred embodiments are also the same.

The alkenyl group represented by R _x and R _y is preferably an allyl group or a vinyl group.

_Rx and _Ry may further have a substituent (for example, substituent T). In this embodiment, for example, R _ox and R _y include a 2-oxoalkyl group or an alkoxycarbonylalkyl group.

Examples of the 2-oxoalkyl group represented by R _x and R _y include those having 1 to 15 carbon atoms (preferably having 1 to 10 carbon atoms), and specifically include a 2-oxopropyl group, And a 2-oxobutyl group.

Examples of the alkoxycarbonylalkyl group represented by R _x and R _y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Further, R _x and R _y may combine to form a ring.

The ring structure formed by connecting R _x and R _y to each other may include an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.

In the general formula (ZI-3), M and R _6c may combine to form a ring structure, and the formed ring structure may include a carbon-carbon double bond.

The compound (ZI-3) is preferably a compound (ZI-3A).

Compound (ZI-3A) is a compound represented by the following general formula (ZI-3A) and having a phenacylsulfonium salt structure.

In the general formula (ZI-3A),

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, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group. , A nitro group, an alkylthio group or an arylthio group.

The R _6c and _{R 7c,} has the same meaning as _{R 6c} and _{R 7c} in the above-mentioned general formula (ZI-3), preferred embodiments thereof are also the same.

The R _x and _{R y,} the same meaning as _{R x} and _{R y} in general formula described above (ZI-3), preferred embodiments thereof are also the same.

Any two or more of R _1c to R _5c , R _x and R _y may be bonded to each other to form a ring structure, and each of the ring structures is independently an oxygen atom, a sulfur atom, an ester bond, It may contain an amide bond or a carbon-carbon double bond. R _5c and R _6c , R _5c and R _x may be bonded to each other to form a ring structure, and this ring structure may each independently contain a carbon-carbon double bond. R _6c and R _7c may be bonded to each other to form a ring structure.

Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic hetero ring, and a polycyclic fused ring in which two or more of these rings are combined. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

_{Examples of} the group formed by combining any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.

As the group formed by 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.

Zc ^- represents an anion.

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

Compound (ZI-4) is represented by the following general formula (ZI-4).

In the general formula (ZI-4),

l represents an integer of 0 to 2.

r represents an integer of 0 to 8.

R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.

When a plurality of R ₁₄ are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a monocyclic or polycyclic cycloalkyl Represents an alkoxy group having a skeleton. These groups may have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. Two R ₁₅ may combine with each other to form a ring.

When two R ₁₅ are bonded to each other to form a ring, the ring skeleton may contain a hetero atom such as an oxygen atom or 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.

Z ⁻ represents an anion.

In the general formula (ZI-4), the alkyl groups of R ₁₃ , R _14, and R ₁₅ are linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. As the alkyl group, a methyl group, an ethyl group, an n-butyl group, a t-butyl group or the like is more preferable.

Next, general formulas (ZII) and (ZIII) will be described.

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

The aryl group of R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

As the alkyl group and cycloalkyl group of R ₂₀₄ to R _207, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, A butyl group and a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (eg, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) are preferable.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may each independently have a substituent. Examples of the substituent which the aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include, for example, an alkyl group (for example, having 1 to 15 carbon atoms) and a cycloalkyl group (for example, having 3 to 15 carbon atoms) 15), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

Z ⁻ represents an anion.

Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^-, Z in the general formula (ZI-3) ^-, Zc in formula (ZI-3A) ^-, and Z in the general formula (ZI-4) ^- as an anion is preferably represented by the following general formula (3).

In the general formula (3),

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

Xf 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.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both 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. When a plurality of R ₄ and R ₅ are present, R ₄ and R ₅ may be the same or different.

The alkyl group represented by R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are preferably a hydrogen atom.

Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (3).

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

Examples of the divalent linking group include -COO-(-C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-,- SO—, —SO ₂ —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms) and a combination of a plurality thereof And a divalent linking group. Among them, -COO -, - OCO -, - CONH -, - NHCO -, - CO -, - O -, - SO 2 -, - COO- alkylene group -, - OCO- alkylene group -, - CONH- alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.

W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable.

Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.

The alicyclic group may be 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. Of these, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, is preferred.

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group and an anthryl group.

The heterocyclic group may be monocyclic or polycyclic. The polycyclic compound can suppress acid diffusion more. 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, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the aforementioned resin. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferred.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (monocyclic, polycyclic, and spirocyclic). Any of which may be used, preferably 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, and a sulfonamide. And sulfonic acid ester groups. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

Formula (3) As the anion represented _{^{_{_{by, SO 3 - -CF 2 -CH 2}}}} -OCO- (L) q'-W, SO 3 - -CF 2 -CHF-CH 2 -OCO- (L) _{^{_{q'-W, SO 3 - -CF}}} 2 -COO- (L) q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L)

q-W, SO ₃ ^-- CF ₂ -CH (CF ₃ ) -OCO- (L) q'-W are preferred. Here, L, q and W are the same as in the general formula (3). q ′ represents an integer of 0 to 10.

In one embodiment, Z in formula (ZI) ^-, Z in the general formula (ZII) ^-, Z in the general formula (ZI-3) ^-, Zc in formula (ZI-3A) ^-, and the general formula (ZI- As Z ^{− in} 4), an anion represented by the following general formula (4) is also preferable.

In the general formula (4),

X ^B1 and X ^B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom. X ^B1 and X ^B2 are preferably a hydrogen atom.

X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. Preferably, at least one of ^XB3 and ^XB4 is a fluorine atom or a monovalent organic group having a fluorine atom, and both ^XB3 and ^XB4 are a fluorine atom or a monovalent organic group having a fluorine atom. Is more preferred. More preferably, both ^XB3 and ^XB4 are alkyl groups substituted with a fluorine atom.

L, q and W are the same as in the general formula (3).

Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^-, Z in the general formula (ZI-3) ^-, Zc in formula (ZI-3A) ^-, and Z in the general formula (ZI-4) ^- it may be a benzenesulfonic acid anion is preferably a benzene sulfonic acid anion which is substituted by a branched alkyl group or a cycloalkyl group.

Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^-, Z in the general formula (ZI-3) ^-, Zc in formula (ZI-3A) ^-, and Z in the general formula (ZI-4) ^- as are preferred aromatic sulfonate anion represented by the following general formula (SA1).

In the formula (SA1),

Ar represents an aryl group, and may further have a substituent other than a sulfonate anion and a-(DB) group. Examples of the substituent that may further have a fluorine atom and a hydroxyl group.

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

D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate group, an ester group, and a group composed of a combination of two or more of these.

B represents a hydrocarbon group.

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

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

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

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

The photoacid generator may be in the form of a low molecular weight compound or may be in a form incorporated into a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.

The photoacid generator is preferably in the form of a low molecular compound.

When the photoacid generator is in the form of a low-molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.

When the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above or may be incorporated in a resin different from the resin (A). .

One photoacid generator may be used alone, or two or more photoacid generators may be used in combination.

In the composition of the present invention, the content of the photoacid generator (when there are a plurality of types, the total thereof) is preferably 0.1 to 35% by mass, and more preferably 0.5 to 35% by mass based on the total solid content of the composition. It is more preferably 25% by mass, further preferably 1 to 20% by mass, particularly preferably 1 to 15% by mass.

When the compound represented by the general formula (ZI-3) or (ZI-4) is contained as the photoacid generator, the content of the photoacid generator contained in the composition (when a plurality of kinds are present, Is preferably 1 to 35% by mass, more preferably 1 to 30% by mass, based on the total solid content of the composition.

<Acid diffusion controller>

The composition of the present invention preferably contains an acid diffusion controller. The acid diffusion controller acts as a quencher for trapping an acid generated from a photoacid generator or the like at the time of exposure and suppressing the reaction of the acid-decomposable resin in the unexposed area due to the 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 No. 2016 / 0070167A1, paragraphs <0095> to <0187> of U.S. Patent Application Publication No. 2015 / 0004544A1, and U.S. Patent Application Publication No. 2016 / 0237190A1. Known compounds disclosed in paragraphs <0403> to <0423> of the specification and paragraphs <0259> to <0328> of US Patent Application Publication No. 2016 / 02744458A1 can be suitably used as acid diffusion controllers. .

As the basic compound (DA), compounds having structures represented by the following formulas (A) to (E) are preferable.

In the general formulas (A) and (E),

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different 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 group. 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.

In the above 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 examples of the partial structure of the proton acceptor functional group include 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 represents a hydrocarbon group, Z ^2c represents a hydrocarbon group, R ⁵² represents an organic group, Y ³ represents an alkylene group, a cycloalkylene group or an arylene group, and Rf contains a fluorine atom. Represents a hydrocarbon group, and M ⁺ independently represents an ammonium cation, a sulfonium cation, or an iodonium cation.

The hydrocarbon group represented by R ⁵¹ may have a substituent.

The hydrocarbon group represented by Z ^2c preferably has 1 to 30 carbon atoms.

The hydrocarbon group represented by Z ^2c may have a substituent. However, in the hydrocarbon group represented by Z ^2c , the carbon atom adjacent to S is preferably not substituted with a fluorine atom.

When Y ³ represents an alkylene group, it may be linear or branched.

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

An onium salt (DC) 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 - represents an anion portion selected from -R ₄ ^-, -SO ₂ -, and ^-N. R ₄ has a carbonyl group (—C (＝ O) —), a sulfonyl group (—S (＝ O) ₂ —), and a sulfinyl group (—S (＝ O) — ) 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. Further, in the general 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),

Rb 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), or an aralkyl group ( It preferably represents 1 to 10 carbon atoms or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be mutually bonded to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb 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 Rb.

As Rb, a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group, or a cycloalkyl group is more preferable.

Examples of the ring formed by two Rb's being connected to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.

Specific examples of the structure of the group represented by formula (d-1) include, but are not limited to, the structure disclosed in paragraph <0466> of US Patent Publication US2012 / 0135348A1.

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

In the general formula (6),

1 represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies 1 + 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.

Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.

In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra may be each independently substituted with the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb. As a good group, it may be substituted with the same group as described above.

Specific examples of the above-mentioned alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra (these groups may be substituted with the above-mentioned groups) include the same groups as those described above for Rb. Can be

Specific examples of the particularly preferable compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012 / 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 US Patent Application Publication No. 2015/0309408 A1.

Preferred examples of the acid diffusion controller are shown below.

In the composition of the present invention, the acid diffusion controller may be used alone or in combination of two or more.

The content of the acid diffusion controller in the composition of the present invention (when a plurality of kinds are present, the total thereof) is preferably 0.05 to 10% by mass, and more preferably 0.05 to 10% by mass, based on the total solid content of the composition. 5 mass% is more preferable.

<Hydrophobic resin>

The composition of the present invention may contain a hydrophobic resin. The hydrophobic resin is preferably a resin different from the resin (A).

When the composition of the present invention contains a hydrophobic resin, the static / dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid followability in immersion exposure, reduce immersion defects, and the like.

The hydrophobic resin is preferably designed so as to be unevenly distributed on the surface of the resist film. However, unlike a surfactant, it is not necessary to have a hydrophilic group in the molecule, and a polar / non-polar substance is uniformly mixed. It does not have to contribute to the task.

The hydrophobic resin is at least one selected from the group consisting of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution on the film surface layer. It is preferable that the resin has a repeating unit having a seed. When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin may be contained in a main chain of the resin or contained in a side chain. You may.

When the hydrophobic resin contains a fluorine atom, the resin preferably has a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group, or a fluorine atom-containing aryl group as a fluorine atom-containing partial structure.

The hydrophobic resin preferably has at least one group selected from the following groups (x) to (z).

(X) acid group

(Y) a group which is decomposed by the action of an alkali developer to increase its solubility in an alkali developer (hereinafter also referred to as a polarity conversion group)

(Z) a group that decomposes under the action of an acid

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

Examples of the group (y) which is decomposed by the action of the alkali developer to increase its solubility in the alkali developer include, for example, a lactone group, a carboxylate group (—COO—), an acid anhydride group (—C (O) OC (O) —), acid imide group (—NHCONH—), carboxylic acid thioester group (—COS—), carbonate ester group (—OC (O) O—), sulfate ester group (—OSO ₂ O—), and Examples include a sulfonic acid ester group (—SO ₂ O—), and a lactone group or a carboxylic acid ester group (—COO—) is preferable. The repeating unit containing these groups is, for example, a repeating unit in which these groups are directly bonded to the main chain of the resin, and includes, for example, a repeating unit of an acrylate ester and a methacrylate ester. In the repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced at the terminal of the resin by using a polymerization initiator or a chain transfer agent having these groups at the time of polymerization. Examples of the repeating unit having a lactone group include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).

The content of the repeating unit having a group (y) which is decomposed by the action of the alkali developer to increase the solubility in the alkali developer is preferably 1 to 100 mol% based on all the repeating units in the hydrophobic resin. The content is more preferably from 3 to 98 mol%, still more preferably from 5 to 95 mol%.

Examples of the repeating unit having a group (z) that decomposes under the action of an acid in the hydrophobic resin include those similar to the repeating unit having an acid-decomposable group described in the resin (A). The repeating unit having a group (z) that decomposes under the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having a group (z) decomposed by the action of an acid is preferably from 1 to 80 mol%, more preferably from 10 to 80 mol%, and more preferably from 20 to 80 mol%, based on all repeating units in the hydrophobic resin. 60 mol% is more preferred. The hydrophobic resin may further have another repeating unit different from the above-mentioned repeating unit.

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

On the other hand, particularly when the hydrophobic resin contains a CH ₃ partial structure in a side chain portion, a form in which the hydrophobic resin does not substantially contain a fluorine atom and a silicon atom is also preferable. Further, it is preferable that the hydrophobic resin be substantially composed of only a repeating unit composed of only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom.

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

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

As the hydrophobic resin, a known resin can be appropriately selected and used alone or as a mixture thereof. For example, known resins disclosed in paragraphs <0451> to <0704> of US Patent Application Publication No. 2015 / 0168830A1, and paragraphs <0340> to <0356> of US Patent Application Publication No. 2016 / 02744458A1 Can be suitably used as a hydrophobic resin. Further, the repeating units disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016 / 0237190A1 are also preferable as repeating units constituting the hydrophobic resin.

Preferred examples of the monomer corresponding to the repeating unit constituting the hydrophobic resin are shown below.

One type of hydrophobic resin may be used alone, or two or more types may be used in combination. It is preferable to use a mixture of two or more types of hydrophobic resins having different surface energies from the viewpoint of compatibility between the immersion liquid followability and the development characteristics in immersion exposure. The content of the hydrophobic resin in the composition is preferably from 0.01 to 10% by mass, more preferably from 0.05 to 8% by mass, based on the total solids in the composition of the present invention.

<Crosslinking agent (G)>

The composition of the present invention may contain a compound capable of crosslinking a resin by the action of an acid (hereinafter, also referred to as a crosslinking agent (G)). Known compounds can be appropriately used as the crosslinking agent (G). For example, known compounds disclosed in paragraphs <0379> to <0431> of U.S. Patent Application Publication No. 2016 / 0147154A1 and paragraphs <0064> to <0141> of U.S. Patent Application Publication No. 2016 / 0282720A1 Can be suitably used as the crosslinking agent (G). The cross-linking agent (G) is a compound having a cross-linkable group capable of cross-linking the resin. Examples of the cross-linkable group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, And an oxetane ring. The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring. The crosslinking agent (G) is preferably a compound (including a resin) having two or more crosslinking groups. The crosslinking agent (G) is more preferably a phenol derivative, a urea compound (compound having a urea structure) or a melamine compound (compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group. The crosslinking agents may be used alone or in combination of two or more. The content of the crosslinking agent (G) is preferably from 1 to 50% by mass, more preferably from 3 to 40% by mass, and still more preferably from 5 to 30% by mass, based on the total solid content of the resist composition.

<Surfactant>

The composition of the present invention preferably contains a surfactant. When a surfactant is contained, a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) Is preferred.

When the composition of the present invention contains a surfactant, a pattern with less adhesion and less development defects can be obtained with good sensitivity and resolution, when using an exposure light source of 250 nm or less, particularly 220 nm or less. . 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 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. More preferred. On the other hand, when the content of the surfactant is 10 ppm (parts per million) or more with respect to the total solid content of the composition, the surface uneven distribution of the hydrophobic resin increases. Thereby, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and the ability to follow water during immersion exposure is improved.

<Resin (J)>

When the composition of the present invention contains a crosslinking agent (G), the composition of the present invention preferably contains an alkali-soluble resin (J) having a phenolic hydroxyl group (also referred to as “resin (J)”). The resin (J) preferably contains a repeating unit having a phenolic hydroxyl group. In this case, typically, a negative pattern is suitably formed. The crosslinking agent (G) may be in a form supported by the resin (J). The resin (J) may contain the acid-decomposable group described above.

The repeating unit having a phenolic hydroxyl group contained in the resin (J) is not particularly limited, but is preferably a repeating unit represented by the following general formula (II).

In the general formula (II),

R ₂ represents a hydrogen atom, an alkyl group which may have a substituent (preferably a methyl group), or a halogen atom (preferably a fluorine atom).

B ′ represents a single bond or a divalent linking group.

Ar ′ represents an aromatic ring group.

m represents an integer of 1 or more. As the resin (J), one type may be used alone, or two or more types may be used in combination. The content of the resin (J) in the total solid content of the composition of the present invention is generally 30% by mass or more.

It is preferably at least 40 mass%, more preferably at least 50 mass%. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. As the resin (J), resins disclosed in paragraphs <0142> to <0347> of US Patent Application Publication 2016 / 0282720A1 can be suitably used.

(Other additives)

The composition of the present invention may further contain an acid proliferating agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, a dissolution accelerator, and the like. As the plasticizer, for example, polyalkylene glycol (the number of carbon atoms in the oxyalkylene unit is preferably 2 to 6, more preferably 2 to 3, and the average number of addition is preferably 2 to 10, preferably 2 to 6. More preferred). Specific examples of the plasticizer include the following.

These plasticizers may be used alone or in combination of two or more. When the composition of the present invention contains a plasticizer, the content of the plasticizer is preferably from 0.01 to 20% by mass, more preferably from 1 to 15% by mass, based on the total solid content of the composition.

<Preparation method>

The solid content concentration of the composition of the present invention is preferably 10% by mass or more, and the upper limit is usually preferably about 50% by mass. The solid content of the composition of the present invention is more preferably 10 to 50% by mass, more preferably 25 to 50% by mass, and still more preferably 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 (resist film) composed of the composition of the present invention is preferably 1 μm or more, for the purpose of increasing the number of processing steps, improving the resistance to implantation, and the like. It is more preferably at least 3 μm, still more preferably at least 5 μm, particularly preferably at least 10 μm. The upper limit is 30 μm or less. In addition, as described later, a pattern can be formed from the composition of the present invention. The thickness of the formed pattern is 1 μm or more, and is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more, for the purpose of increasing the number of processing steps and improving the resistance to implantation. The upper limit is 30 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. Further, when the solid content concentration of the composition of the present invention is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.2 μm or less, and 0.1 μm or less. More preferred. 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 1000 mPa · s. The viscosity of the composition of the present invention is more preferably 100 to 600 mPa · s from the viewpoint of more excellent coatability. The viscosity can be measured by an E-type viscometer.

<Application>

The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change 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) a step of forming a resist film (actinic ray-sensitive or radiation-sensitive film) 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) a step of developing the exposed resist film using a developing solution (developing step).

The pattern forming method of the present invention is not particularly limited as long as it includes the above steps (i) to (iii), and may further include the following steps. In the pattern forming method of the present invention, (ii) the exposure method in the exposure step may be immersion exposure. 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 (i) resist film forming step, (ii) exposing step, and (iii) developing step can be performed by a generally known method.

In the pattern forming method of the present invention, the thickness of the actinic ray-sensitive or radiation-sensitive film formed on the substrate in the (i) resist film forming step is preferably 1 μm or more as described above, preferably 3 μm. The above is more preferable, 5 μm or more is further preferable, and 10 μm or more is particularly preferable. The upper limit is 30 μm or less. 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, those containing the above-mentioned acid diffusion controller are preferable. A protective film may be formed on the resist film containing the hydrophobic resin described above.

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. A substrate can be used. Specific examples of the support include an inorganic substrate such as silicon, SiO ₂ , and SiN.

The heating temperature is preferably from 70 to 150 ° C., more preferably from 70 to 130 ° C., still more preferably from 80 to 130 ° C., and further preferably from 80 to 120 ° C. in both (iv) the pre-heating step and (v) the post-exposure heating step. Is most preferred. The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, 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, far ultraviolet light is preferable, and the wavelength is preferably 1 to 300 nm, more preferably 100 to 300 nm, and further preferably 200 to 300 nm. Specifically, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, an EUV (13 nm), an electron beam, and the like are used. , EUV or an electron beam is preferable, and a KrF excimer laser is more preferable.

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

As the alkali developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used. In addition, an alkaline aqueous solution such as an inorganic alkali, a primary to tertiary amine, an alcoholamine, and a cyclic amine is also 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 an alkali developer is usually 10 to 300 seconds. The alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.

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

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

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

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

A plurality of the above-mentioned solvents may be mixed, or a solvent other than the above or water may be mixed. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and more preferably 95 to 100% by mass based on the total amount of the developer. % Is particularly preferred.

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

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

The organic developer may contain the acid diffusion controller described above.

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) or a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispense method). Can be

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

(Iii) It is preferable to include a step of washing with a rinsing 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 rinsing liquid used in the rinsing step after the developing step using a developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a general solution containing an organic solvent can be used. As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. Is preferred. Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent include those similar to those described for the developer containing an organic solvent. In this case, the rinsing liquid used in the rinsing step is more preferably a rinsing liquid containing a monohydric alcohol.

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

Each component may be used as a mixture of a plurality of components or as a mixture with an organic solvent other than those described above. The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The rinsing liquid may contain an appropriate amount of a surfactant. In the rinsing step, the substrate that has been developed using the organic developing solution is subjected to a cleaning process using a rinsing solution containing an organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (rotation coating method), or immersing the substrate in a bath filled with the rinsing liquid for a predetermined time A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be given. In particular, it is preferable to perform a cleaning process by a spin coating method, and after the cleaning, rotate the substrate at a rotation speed of 2,000 to 4,000 rpm (revolution per minute) to remove the rinsing liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. By this heating step, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is usually 40 to 160 ° C, preferably 70 to 120 ° C, more preferably 70 to 95 ° C, and the heating time is usually 10 seconds to 3 minutes, and 30 seconds to 30 minutes. 90 seconds is preferred.

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 various materials is preferably 1 ppm or less, more preferably 100 ppt (parts per trillion) or less, still more preferably 10 ppt or less, and substantially no content (detection limit of the measuring device). The following 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 reduced eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Unexamined Patent Application Publication No. 2016-201426) 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, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (JP-A-2016-206500). Further, as a method of reducing impurities such as metals contained in the various materials, select a material having a low metal content as a material constituting the various materials, perform a filter filtration on the materials constituting the various materials, Alternatively, there is a method in which distillation is performed under conditions where 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 various materials described above are described in U.S. Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Laid-Open No. 2015-123351), and the like in order to prevent impurities from being mixed. It is preferably stored in a container.

A method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. As a method 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), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. A known method as described in 8328 83280N-1 “EUV Resist Curing Technology for LWR Reduction and Etch Selection Enhancement” may be applied. Further, the pattern formed by the above-mentioned 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.

[Method of Manufacturing Electronic Device] The present invention also relates to a method of 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, usage 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.

<Resin>

About the resin used, the structure of a repeating unit and its content (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) are shown. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). The content of the repeating unit was measured by ¹³ C-NMR (nuclear magnetic resonance).

For each resin, the content (mol%) of the repeating unit (a1) derived from a monomer (monomer a1) having a glass transition temperature of 50 ° C. or lower when formed into a homopolymer, the type of the monomer a1, and the monomer a1 When the polymer has a glass transition temperature (Tg), a kind of the monomer corresponding to the repeating unit (a2) having an acid-decomposable group, the content of the repeating unit (a2), Table 2 shows the type of the corresponding monomer, the content of the repeating unit (a4), the type of the monomer corresponding to the other repeating unit, and the content of the other repeating unit.

(Method of Measuring Glass Transition Temperature of Homopolymer) The glass transition temperature of a homopolymer takes a catalog value or a literature value when there is a catalog value, and when there is no, a differential scanning calorimetry (DSC) method. Was measured by The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg was 18,000, and the degree of dispersion (Mw / Mn) was 1.7. As a DSC apparatus, a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Co., Ltd. was used, and the temperature was measured at a heating rate of 10 ° C./min. The homopolymer used for the measurement of Tg was synthesized using the corresponding monomer by the following procedure. The synthesis of the homopolymer is carried out by a general drop polymerization method. 54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was heated to 80 ° C. under a nitrogen stream. While stirring this solution, 125 parts by mass of a PGMEA solution containing 21% by mass of the corresponding monomer and 0.35% by mass of dimethyl 2,2′-azobisisobutyrate were added dropwise over 6 hours. After the completion of the dropwise addition, the mixture was further stirred at 80 ° C. for 2 hours. After allowing the reaction solution to cool, it is reprecipitated with a large amount of methanol / water (mass ratio 9: 1), filtered, and the obtained solid is dried to obtain a homopolymer (Mw: 18000, Mw / Mn: 1.7). I got The obtained homopolymer was subjected to DSC measurement. The DSC apparatus and the heating rate were as described above.

The glass transition temperature when the monomer (ME-2) corresponding to other repeating units contained in the resin AX-1 was a homopolymer was 100 ° C.

<Solvent>

Table 3 shows the types, boiling points and viscosities of the solvents used. PGMEA represents propylene glycol monomethyl ether acetate, and PGME represents propylene glycol monomethyl ether.

<Photoacid generator>

The structure of the photoacid generator used is shown below.

<Acid diffusion controller>

The acid diffusion controller used is shown below.

<Surfactant>

The surfactants used are shown below.

WA: PF6320 manufactured by OMNOVA

WB: PF636 manufactured by OMNOVA

WC: TF-R41 manufactured by DIC

Salicylic acid was used as another additive.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>

Each component shown in Table 4 was mixed to obtain the solid content concentration (% by mass) shown in Table 4 to obtain a solution. Next, the obtained solution is filtered through a polyethylene filter having a pore size of 3 μm to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) res-1 to res-20, res-1X to res -9X was prepared. In the resist composition, the solid content means all components other than the solvent. 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, and Zr) were measured using an ICP-MS device (Inductively Coupled Plasma Mass Spectrometer) “Agilent 7500cs” manufactured by Agilent Technologies. The content of each metal species was as follows. Each was less than 10 ppb (parts-per-billion).

In Table 4, the content (% by mass) of each component other than the solvent means the content ratio to the total solid content.

[Pattern formation and various evaluations]

<Pattern formation>

Using a spin coater “ACT-8” manufactured by Tokyo Electron, a resist composition prepared without applying an antireflection layer was applied to a hexamethyldisilazane-treated Si substrate (manufactured by Advanced Materials Technology). Then, heating and drying were performed at 130 ° C. for 60 seconds to form a positive resist film having a thickness of 10 μm. Using a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C wavelength: 248 nm), the resist film is passed through the following mask at the following optimum exposure dose, NA (numerical aperture) = 0.68, σ = 0. Pattern exposure was performed under 60 exposure conditions. After the irradiation, the film was baked at 130 ° C. for 60 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. Exposure is performed through a mask having a line and space pattern such that the space pattern after the reduced projection exposure is 3 μm and the pitch is 33 μm, and the exposure amount is such that the formed space pattern is 3 μm and the pitch is 33 μm. Exposure (sensitivity) (mJ / cm ² ). The measurement of the space pattern width was performed using a scanning electron microscope (SEM) (9380I manufactured by Hitachi, Ltd.). According to the above procedure, an evaluation pattern wafer having a substrate and a pattern (resist pattern) formed on the substrate surface was obtained.

<Viscosity of resist composition>

The viscosity of the prepared resist composition was measured at 25.0 ° C. using RE-85L manufactured by TOKISANGYO.

<Evaluation of crack generation>

In a chamber in a CD-SEM (Critical Dimension-Scanning Electron Microscope), a vacuum process (evacuation) was performed on the evaluation pattern wafer for 60 seconds. The pressure in the chamber was set to be 0.002 Pa. After the vacuum treatment, the pattern wafer for evaluation was observed with an optical microscope, and the presence or absence of cracks was evaluated. Specifically, cracks in the pattern formed on the substrate surface were confirmed, and evaluated based on the following criteria.

A: No crack

B: 1 to 10 cracks

C: 11 to 20 cracks

D: 21 to 30 cracks

E: 31 or more cracks

<Evaluation of void generation>

Using a spin coater “ACT-8” manufactured by Tokyo Electron, a resist composition prepared without applying an anti-reflection layer was applied to a hexamethyldisilazane-treated Si substrate (manufactured by Advanced Materials Technology). Then, the substrate was dried and baked to form a resist film on the substrate. A substrate (wafer) having a resist film is set in a dry etching apparatus (U-621, manufactured by Hitachi High-Technologies Corporation), and a gas pressure of gas mixture of CF ₄ , Ar, and N ₂ (gas ratio, 1:10:10) is applied. Etching for 30 seconds under the conditions of ₄ Pa, plasma power of 1600 W and substrate bias of 1200 W, and a gas mixture of O ₂ and CF ₄ (gas ratio: 20: 1) at a gas pressure of 2 Pa, plasma power of 800 W and substrate bias of 0 W. The etching process was continued for 60 seconds, and the etching process was repeated six times in each case. The wafer after the etching treatment was broken, and the cross section of the resist film was observed at a magnification of 10,000 using a scanning electron microscope (SEM) (S-4800, manufactured by Hitachi High-Technologies Corporation). The observed voids (voids) in the resist film were confirmed, and criteria were set as follows.

A: No void

B: 1 to 5 voids

C: 6 to 15 voids

D: 16 to 25 voids

E: 26 or more voids

<Evaluation of PCD performance>

Using a spin coater “ACT-8” manufactured by Tokyo Electron, a resist composition prepared without applying an anti-reflection layer was applied to a hexamethyldisilazane-treated Si substrate (manufactured by Advanced Materials Technology). Then, the substrate was dried and baked to form a resist film on the substrate. Thereafter, the substrates each having the resist film were stored for a certain time in a clean room environment (this time is referred to as “storage time”). Thereafter, the resist film after storage was subjected to pattern exposure using a KrF excimer laser scanner at the following optimum exposure amount through the following mask. After the irradiation, the film was baked at 130 ° C. for 60 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. Exposure is performed through a mask having a line and space pattern such that the space pattern after the reduced projection exposure is 3 μm and the pitch is 33 μm, and the exposure amount is such that the formed space pattern is 3 μm and the pitch is 33 μm. Exposure (sensitivity) (mJ / cm ² ). The measurement of the space pattern width was performed using a scanning electron microscope (SEM) (9380I manufactured by Hitachi, Ltd.). The longest storage time in which the space width of the obtained pattern was within the range of 3 μm ± 30 nm was defined as “PCD time”, and the evaluation was made based on the following criteria.

A: PCD time is 60 minutes or more

B: PCD time is 30 minutes or more and less than 60 minutes

C: PCD time is less than 30 minutes

From the results shown in Table 5, it can be seen that the resist compositions of the examples have excellent PCD performance, do not cause cracks in the pattern during etching, and do not generate voids inside the pattern.

Claims

An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A), a solvent (B), and a compound that generates an acid upon irradiation with actinic rays or radiation,

The resin (A) includes a repeating unit (a1) derived from a monomer having a glass transition temperature of 50 ° C. or lower when formed into a homopolymer, and a repeating unit (a2) having an acid-decomposable group,

The repeating unit (a1) is a non-acid-decomposable repeating unit,

The resin (A) has a repeating unit having an aromatic ring,

The solvent (B) has a boiling point of 135 ° C. or less and a viscosity of 1.5 mPa · s or less, and is used for forming a film having a thickness of 1 to 30 μm. Composition.
2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a1) is a repeating unit represented by the following general formula (1-2).

In the general formula (1-2), R 1 represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R 2 represents a non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a hetero atom in the chain.
2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a1) is a repeating unit represented by the following general formula (1-3).

In the general formula (1-3), R 3 represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R 4 may be a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group which may contain a hetero atom in the chain, or a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group which may contain a hetero atom in the ring member. Represents an acid-decomposable cycloalkyl group.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the viscosity of the solvent (B) is 1.2 mPa · s or less.
The actinic ray-sensitive or radiation-sensitive resin according to any one of claims 1 to 4, wherein the solvent (B) is at least one selected from an aromatic solvent, a ketone solvent, and an ester solvent. Composition.
The actinic ray according to any one of claims 1 to 5, wherein the solvent (B) is at least one selected from methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, ethyl acetate, isobutyl acetate, and butyl acetate. Or radiation-sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein the solvent (B) is at least one selected from methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone.
The actinic ray according to any one of claims 1 to 7, wherein the content of the solvent (B) is 20% by mass or more based on the total amount of the solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition. Or radiation-sensitive resin composition.
(I) a step of forming an actinic ray-sensitive or radiation-sensitive film having a thickness of 1 to 30 μm on a substrate with the actinic ray-sensitive or radiation-sensitive resin composition;

(Ii) irradiating the actinic ray-sensitive or radiation-sensitive film with actinic ray or radiation, and

(Iii) a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation using a developer.

A pattern forming method, wherein the actinic ray-sensitive or radiation-sensitive resin composition is the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8.
A resist film having a film thickness of 1 to 30 μm, formed by the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8.
A method for manufacturing an electronic device, comprising the pattern forming method according to claim 9.