KR102588117B1 - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and electronic device manufacturing method - Google Patents

Abstract

환 Q₁은 4~6원환이다. 단, 환 Q₁은 다른 환과 축합환을 형성하고 있어도 된다.
환 Q₁은 환원으로서 적어도 2개의 탄소 원자를 갖고, S⁺와 직결하는 환원의 원자는 탄소 원자이다. R^P1~R^P5는 각각 독립적으로 수소 원자, 수산기, 할로젠 원자, 알킬기, 아릴기, 헤테로아릴기, 또는 알콕시기를 나타낸다. R^P1~R^P5 중 적어도 2개가 결합하여 환을 형성해도 된다. Z^-는, 비구핵성 음이온을 나타낸다.A resin containing a non-acid-decomposable repeating unit derived from a monomer with a glass transition temperature of 50°C or lower when converted into a homopolymer and a repeating unit having an acid-decomposable group, and a compound represented by general formula (P-1) an actinic ray-sensitive or radiation-sensitive resin composition, a resist film formed by the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and electronic This is a method of manufacturing a device.

Ring Q ₁ is a 4- to 6-membered ring. However, ring Q ₁ may form a condensed ring with another ring.
Ring Q ₁ has at least two carbon atoms as a reduction, and the reduction atom directly connected to S ⁺ is a carbon atom. R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group. At least two of R ^P1 to R ^P5 may combine to form a ring. Z ^- represents a non-nucleophilic anion.

Description

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

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

Since resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for resist to compensate for the decrease in sensitivity due to light absorption. For example, in the image forming method of positive chemical amplification, the photoacid generator in the exposed area is decomposed to produce acid by exposure to excimer laser, electron beam, extreme ultraviolet light, etc., and then the photoacid generator is decomposed to generate acid, and the photoacid generator is decomposed to produce acid in the post-exposure bake (PEB: PostExposureBake). An example is an image forming method in which the generated acid is used as a reaction catalyst to change alkali-insoluble groups into alkali-soluble groups, and the exposed portion is removed using an alkaline developer.

Meanwhile, these days, miniaturization using the wavelength of the exposure light source is facing limitations, and especially for ion implantation process applications and NAND memory (NOT AND memory), three-dimensionalization of the memory layer is becoming mainstream for the purpose of increasing capacity. . Since three-dimensionalization of the memory layer requires an increase in the number of processing steps in the vertical direction, the resist film is required to be thickened from the conventional nano size to the micron size.

For example, Patent Documents 1 and 2 describe a chemically amplified positive photoresist composition for thick films used to form a thick film photoresist layer.

Patent Document 1: Japanese Patent Publication No. 2007-206425 Patent Document 2: Japanese Patent Publication No. 2008-191218

However, as a result of etching the object to be etched using a thick film pattern formed by lithography from the resist composition described in Patent Document 1 or 2 as a mask, voids were discovered inside the pattern. There were two types of voids: voids with a size of 50 nm or more (also called "large voids") and voids with a size of less than 50 nm (also called "small voids").

Therefore, the present invention provides an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern in which large voids and small voids are unlikely to occur inside the pattern during etching, and the actinic ray-sensitive or radiation-sensitive resin. The object is to provide a resist film formed from the composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a manufacturing method of an electronic device.

As a result of intensive studies to solve the above problems, the present inventors have developed an actinic ray-sensitive product containing a specific resin and a compound with a specific structure (acid generator with a specific structure) that generates an acid upon irradiation of actinic rays or radiation. Alternatively, a radiation-sensitive resin composition was found to be able to solve the above problems, and the present invention was completed.

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

<1>

An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) and a compound that generates acid upon irradiation of 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 converted into a homopolymer, and a repeating unit (a2) having an acid-decomposable group,

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

An actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound that generates acid upon irradiation of actinic rays or radiation includes a compound represented by the following general formula (P-1).

[Formula 1]

In the general formula (P-1),

Q ₁ represents a ring containing S ⁺ .

Ring Q ₁ is a 4-membered ring, a 5-membered ring, or a 6-membered ring. However, ring Q ₁ may form a condensed ring with another ring.

Ring Q ₁ has at least two carbon atoms as a reduction, and the reduction atom directly connected to S ⁺ is a carbon atom.

R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group. At least two of R ^P1 to R ^P5 may combine to form a ring.

Z ^- represents a non-nucleophilic anion.

<2>

The actinic ray-sensitive or radiation-sensitive resin composition according to <1>, wherein Q ₁ is a non-aromatic ring.

<3>

The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <2>, wherein Q ₁ has a hetero atom other than S ⁺ as a reduction.

<4>

The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <2>, wherein the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-2).

[Formula 2]

In the general formula (P-2),

R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group. At least two of R ^P1 to R ^P5 may combine to form a ring.

R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent.

m1 and m2 each independently represent 1 or 2.

When there are multiple R ^P6 to R ^P9 , they may be the same or different.

When m1 represents 2, two R ^P6 may combine to form a ring.

When m2 represents 2, two R ^P8s may combine to form a ring.

M ₁ represents a heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.

Z ^- represents a non-nucleophilic anion.

<5>

The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <2>, wherein the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-3).

[Formula 3]

In the general formula (P-3),

R ^P1 , R ^P2 , R ^P4 , and R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group.

R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent.

m1 and m2 each independently represent 1 or 2.

When there are multiple R ^P6 to R ^P9 , they may be the same or different.

When m1 represents 2, two R ^P6 may combine to form a ring.

When m2 represents 2, two R ^P8s may combine to form a ring.

M ₁ represents a heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.

R ^P12 represents a hydrogen atom or an alkyl group.

At least two of R ^P1 , R ^P2 , R ^P4 , R ^P5 , and R ^P12 may combine to form a ring.

Z ^- represents a non-nucleophilic anion.

<6>

The actinic ray sensitive or radiation sensitive compound according to any one of <1> to <5>, wherein the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-4) or (P-5). Sex resin composition.

[Formula 4]

[Formula 5]

In the general formulas (P-4) and (P-5),

R ^P1 , R ^P2 , R ^P4 , and R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group.

R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent.

R ^P6 to R ^P9 that exist in plural may be the same or different.

Two R ^P6s may combine to form a ring.

Two R ^P8s may combine to form a ring.

M ₁ represents a heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.

R ^P12 represents a hydrogen atom or an alkyl group.

At least two of R ^P1 , R ^P2 , R ^P4 , R ^P5 , and R ^P12 may combine to form a ring.

Z ^- represents a non-nucleophilic anion.

In the general formula (P-5), R ^P13 represents a hydrogen atom or a substituent.

<7>

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <6>, wherein the solid content concentration is 10% by mass or more.

<8>

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <7>, wherein Z ^- is an anion represented by any of the following general formulas (Z1) to (Z4).

[Formula 6]

In general formula (Z1), R ^Z1 represents an alkyl group.

[Formula 7]

In general formula (Z2),

Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Multiple Xfs may be the same or different.

R ^Z2 and R ^Z3 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. When there are multiple R ^Z2 and R ^Z3 , each may be the same or different.

L ^Z1 represents a divalent linking group, and when two or more L ^Z1s exist, they may be the same or different.

A ^Z1 represents an organic group containing a cyclic structure.

x represents an integer from 1 to 20, and y represents an integer from 0 to 10. z represents an integer from 0 to 10.

[Formula 8]

In general formulas (Z3) and (Z4), Rb ₃ to Rb ₇ each independently represent an alkyl group, a cycloalkyl group, or an aryl group. Rb ₃ and Rb ₄ may combine to form a ring structure. Rb ₅ and Rb ₆ may combine to form a ring structure.

<9>

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <8>, wherein the resin (A) has a repeating unit having an aromatic ring.

<10>

A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <9>.

<11>

(i) A process of forming an actinic ray-sensitive or radiation-sensitive film with a film thickness of 1 μm or more on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition,

(ii) a process of irradiating actinic rays or radiation with a wavelength of 200 to 300 nm to the actinic ray-sensitive or radiation-sensitive film, and

(iii) A pattern forming method comprising the step of developing the actinic ray or radiation sensitive film irradiated with actinic ray or radiation using a developer,

The actinic ray-sensitive or radiation-sensitive resin composition is an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) and a compound that generates an acid upon irradiation of 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 converted 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 pattern forming method wherein the compound that generates acid upon irradiation of actinic rays or radiation is an actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the following general formula (P-1).

[Formula 9]

In the general formula (P-1),

Q ₁ represents a ring containing S ⁺ .

Ring Q ₁ is a 4-membered ring, a 5-membered ring, or a 6-membered ring. However, ring Q ₁ may form a condensed ring with another ring.

Ring Q ₁ has at least two carbon atoms as a reduction, and the reduction atom directly connected to S ⁺ is a carbon atom.

R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group. At least two of R ^P1 to R ^P5 may combine to form a ring.

Z ^- represents a non-nucleophilic anion.

<12>

A method of manufacturing an electronic device comprising the pattern forming method according to <11>.

According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern in which large voids and small voids are unlikely to occur inside the pattern during etching, and the actinic ray-sensitive or radiation-sensitive resin composition. A resist film formed by this method, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a manufacturing method of an electronic device can be provided.

Hereinafter, the present invention will be described in detail.

The description of the structural requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

“Active rays” or “radiation” in this specification include, for example, the bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer lasers, extreme ultraviolet (EUV) rays, X-rays, soft X-rays, and electron beam (EB). “Light” in this specification means actinic rays or radiation. In this specification, unless otherwise specified, “exposure” refers not only to exposure by the bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV), and X-rays, but also exposure by electron beams, ion beams, etc. It also includes drawing using particle beams.

In this specification, "~" is used to mean that the numerical values written before and after it are included as the lower limit and the upper limit.

In this specification, (meth)acrylate represents at least one type of acrylate and methacrylate. Moreover, (meth)acrylic acid represents at least one type of acrylic acid and methacrylic acid.

In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion (also referred to as molecular weight distribution) (Mw/Mn) of the resin are measured using a GPC (Gel Permeation Chromatography) device (HLC- manufactured by Tosoh Corporation). 8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL/min, detector: differential refractive index. It is defined as a polystyrene conversion value using a Refractive Index Detector.

Regarding the notation of groups (atomic groups) in this specification, notations that do not describe substitution or unsubstitution include groups that have a substituent as well as groups that do not have a substituent. For example, “alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group). In addition, "organic group" in this specification refers to a group containing at least one carbon atom.

In addition, in this specification, when “may have a substituent”, the type of substituent, the position of the substituent, and the number of substituents are not particularly limited. The number of substituents may be, for example, 1, 2, 3, or more. Examples of substituents include monovalent non-metallic atom groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.

(substituent T)

Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; Alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; Aryloxy groups such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; Acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; Acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxyl group; alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; Arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; Alkyl group; Cycloalkyl group; Aryl group; heteroaryl group; hydroxyl group; carboxylic acid; form diary; tongue group; Cyano group; Alkylaminocarbonyl group; Arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; Arylamino groups and combinations thereof may be included.

[Active 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 “the composition of the present invention”) contains a resin (A) and a compound that generates an acid upon irradiation of actinic rays or radiation. An actinic ray-sensitive or radiation-sensitive resin composition, wherein the resin (A) includes a repeating unit (a1) derived from a monomer having a glass transition temperature of 50° C. or lower when converted into a homopolymer, and a repeating unit having an acid-decomposable group. (a2), the repeating unit (a1) is a non-acid-decomposable repeating unit, and the compound that generates acid upon irradiation of actinic rays or radiation includes a compound represented by the following general formula (P-1) It is an actinic ray-sensitive or radiation-sensitive resin composition.

[Formula 10]

In the general formula (P-1),

Q ₁ represents a ring containing S ⁺ .

Ring Q ₁ is a 4-membered ring, a 5-membered ring, or a 6-membered ring. However, ring Q ₁ may form a condensed ring with another ring.

Ring Q ₁ has at least two carbon atoms as a reduction, and the reduction atom directly connected to S ⁺ is a carbon atom.

R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group. At least two of R ^P1 to R ^P5 may combine to form a ring.

Z ^- represents a non-nucleophilic anion.

The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Moreover, the resist composition for alkaline development may be sufficient, or the resist composition for organic solvent development may be used. Among them, it is preferable that it is a positive resist composition and that it is a resist composition for alkaline development.

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

The composition of the present invention may or may not contain a crosslinking agent (a compound that crosslinks the resin (A) by the action of an acid), but it is preferable that it does not contain a crosslinking agent.

The reason why the composition of the present invention can form a pattern in which large voids and small voids are unlikely to occur inside the pattern during etching is not clear in detail, but is assumed as follows.

A resist film is formed using a resist composition containing an acid-decomposable resin and a photoacid generator, and the photoacid generator usually remains in the pattern (resist pattern) obtained through exposure and alkali development. And in processes such as vacuum suction performed when etching an object to be etched (typically plasma etching) using this pattern as a mask, large voids and small voids are formed due to the decomposition product of the photoacid generator remaining inside the pattern. knew what was happening.

The present inventors used a resin (resin (A)) having a repeating unit (repeating unit (a1)) derived from a monomer whose glass transition temperature when converted into a homopolymer is 50° C. or lower as an acid-decomposable resin (resin (A)), thereby forming a pattern. We examined improving the plasticity of . As a result, the decomposition product of the photoacid generator could be easily removed from the inside of the pattern by volatilization, and large voids could be reduced.

However, even when resin (A) was used, there was room for improvement in reducing small voids.

Accordingly, the present inventors studied carefully and thought that if the cation of the photoacid generator decomposed by exposure is highly volatile, it volatilizes before etching and does not remain inside the pattern, thereby suppressing the generation of voids during etching. And, it was found that not only large voids but also small voids can be significantly reduced by using the resin (A) together with a photoacid generator represented by general formula (P-1). In particular, it was found that according to the present invention, even extremely small voids with a size of less than 20 nm can be reduced.

In addition, in the acid-decomposable resin (resin (A)) in the present invention, the repeating unit (a1) is a non-acid-decomposable repeating unit. This means that, in cases where the repeating unit derived from a monomer with a glass transition temperature of 50°C or lower when used as a homopolymer is an acid-decomposable repeating unit (for example, a repeating unit derived from tert-butyl acrylate), the present invention It is based on the inability to exert its effect. That is, under the etching environment, the photoacid generator remaining inside the pattern is decomposed to generate acid, and a deprotection reaction of the remaining acid-decomposable repeating unit proceeds. For example, a repeating unit derived from tert-butyl acrylic acid undergoes a deprotection reaction to become a repeating unit derived from acrylic acid. Here, since acrylic acid is a monomer whose glass transition temperature when used as a homopolymer is higher than 50°C, it is thought that the plasticity of the pattern cannot be improved and the void reduction effect is not obtained.

<Resin (A)>

Resin (A) contained in the composition of the present invention includes a repeating unit (a1) derived from a monomer having a glass transition temperature (Tg) of 50° C. or lower when converted into a homopolymer, and a repeating unit (a2) having an acid-decomposable group. It includes, and the repeating unit (a1) is a non-acid-decomposable repeating unit.

Resin (A) is a resin (acid-decomposable resin) that decomposes under the action of acid and increases polarity because it contains a repeating unit having an acid-decomposable group. That is, in the pattern forming method of the present invention described later, typically, when an alkaline developer is used as the developer, a positive pattern is suitably formed, and when an organic developer is used as the developer, a negative pattern is formed. Formed appropriately.

(repetition unit (a1))

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

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

(Method for measuring glass transition temperature of homopolymer)

The glass transition temperature of the homopolymer is taken from a catalog or literature value if available, and if not, measured by differential scanning calorimetry (DSC). The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg is set to 18000, and the dispersion degree (Mw/Mn) is set to 1.7. As the DSC device, a thermal analysis DSC differential scanning calorimeter type Q1000 manufactured by TA Instrument Japan Co., Ltd. was used, and the temperature increase rate was measured at 10°C/min.

In addition, the homopolymer used for measuring Tg can be synthesized by a known method using the corresponding monomer, for example, by a general dropping 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 mass% of the corresponding monomer and 0.35 mass% of dimethyl 2,2'-azobisisobutyrate was added dropwise over 6 hours. After the dropwise addition was completed, the mixture was stirred at 80°C for an additional 2 hours. After the reaction solution was left to cool, it was reprecipitated with a large amount of methanol/water (mass ratio 9:1), filtered, and the obtained solid was dried to obtain a homopolymer (Mw: 18000, Mw/Mn: 1.7). The obtained homopolymer was subjected to DSC measurement. The DSC device and temperature increase rate were as described above.

The monomer a1 is not particularly limited as long as the glass transition temperature (Tg) when used as a homopolymer is 50°C or lower, and from the viewpoint of reducing voids inside the pattern, it is preferable that the Tg when used as a homopolymer is 30°C or lower. The lower limit of Tg when monomer a1 is used as a homopolymer is not particularly limited, and is preferably -80°C or higher, more preferably -70°C or higher, further preferably -60°C or higher, and particularly preferably -50℃ or higher.

The repeating unit (a1) is preferably a repeating unit having a non-acid-decomposable alkyl group of 2 or more carbon atoms, which may contain a heteroatom in the chain, because the low molecular weight compound remaining in the film can be easily volatilized to the outside of the system. . As used herein, “non-acid decomposable” means that the photoacid generator has the property of not causing a desorption/decomposition reaction due to the acid generated.

That is, the term "non-acid decomposable alkyl group" refers, more specifically, to an alkyl group that is not decomposed from the resin (A) by the action of the acid generated by the photo acid generator, or an alkyl group that is not decomposed by the action of the acid generated by the photo acid generator. I can hear it.

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

Hereinafter, 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, will be described.

The non-acid-decomposable alkyl group having 2 or more carbon atoms that may contain a hetero atom in the chain is not particularly limited, but examples include an alkyl group having 2 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms that contains a hetero atom in the chain. I can hear it.

Examples of the alkyl group having 2 to 20 carbon atoms containing a hetero atom in the chain include, for example, one or two or more -CH ₂ -, -O-, -S-, -CO-, -NR ₆ -, or 2 of these. Examples of alkyl groups substituted with the above-mentioned divalent organic groups include. Said R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Non-acid-decomposable alkyl groups having two or more carbon atoms that may contain heteroatoms in the chain specifically include ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, uryl group, stearyl group, isobutyl group, sec-butyl group, 1-ethylpentyl group and 2-ethylhexyl group, and one or two or more of them -CH ₂ - is -O- or -O-CO A monovalent alkyl group substituted with - can be mentioned.

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

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

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

[Formula 11]

In 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, and examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group represented by R ₁ is not particularly limited, and examples include alkyl groups having 1 to 10 carbon atoms, and specific examples include methyl group, ethyl group, and 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, and examples include cycloalkyl groups having 5 to 10 carbon atoms, and more specifically, cyclohexyl groups.

As R ₁ , a hydrogen atom or a methyl group is particularly preferable.

The definition and suitable 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 carboxyl group or hydroxyl group, which may contain a hetero atom in the chain, or a reduction-resistant alkyl group, since the low molecular weight compound remaining in the film can easily be volatilized to the outside of the system. It may be a repeating unit having a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group, which may contain a hetero atom.

Hereinafter, a repeating unit having 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 cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the chain, is explained. do.

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

The number of carbon atoms 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 less, the upper limit of the number of carbon atoms of the non-acid decomposable alkyl group is preferably, for example, 20 or less.

The non-acid-decomposable alkyl group that may contain a hetero atom in the chain is not particularly limited, and examples include an alkyl group with 2 to 20 carbon atoms and an alkyl group with 2 to 20 carbon atoms that contains a hetero atom in the chain. Additionally, 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, for example, one or two or more -CH ₂ -, -O-, -S-, -CO-, -NR ₆ -, or 2 of these. Examples of alkyl groups substituted with the above-mentioned divalent organic groups include. Said R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The number of carbon atoms of the non-acid-decomposable alkyl group, which may contain a hetero atom in the chain, is preferably 2 to 16, more preferably 2 to 10, and even more preferably 2 to 8 from the viewpoint of suppressing voids inside the pattern.

Additionally, 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 carboxyl group and containing a hetero atom in the chain include, for example, a repeating unit having the following structure.

[Formula 12]

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, preferably 20 or less, and 16 or less. It is more preferable that it is 10 or less.

The non-acid-decomposable cycloalkyl group that may contain a hetero atom in the reduction is not particularly limited, and examples include cycloalkyl groups having 5 to 20 carbon atoms (more specifically, cyclohexyl groups) and those containing a hetero atom in the reduction. A cycloalkyl group having 5 to 20 carbon atoms is included. Additionally, at least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxy group or a hydroxyl group.

Examples of the cycloalkyl group having 5 to 20 carbon atoms containing a hetero atom include, for example, one or two or more -CH ₂ -, -O-, -S-, -CO-, -NR ₆ -, or these. Examples include cycloalkyl groups substituted with a divalent organic group in combination of two or more. Said R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

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

As repeating units having 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 cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the chain, the repeating units of the present invention include: Since the effect is more excellent, the repeating unit represented by the following general formula (1-3) is especially preferable.

[Formula 13]

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

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

Definition and suitable embodiments of a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in the chain represented by R ₄ , or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom during reduction is the same as described above.

Among them, as R ₄ , a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom for reduction, is preferable.

As monomer a1, for example, ethyl acrylate (-22°C), n-propyl acrylate (-37°C), isopropyl acrylate (-5°C), n-butylacrylate (-55°C), n- Butyl methacrylate (20℃), n-hexyl acrylate (-57℃), n-hexyl methacrylate (-5℃), n-octyl methacrylate (-20℃), 2-ethylhexyl acrylate (-70℃), isononyl acrylate (-82℃), lauryl methacrylate (-65℃), 2-hydroxyethyl acrylate (-15℃), 2-hydroxypropyl methacrylate ( 26°C), 1-[2-(methacryloyloxy)ethyl] succinic acid (9°C), 2-ethylhexyl methacrylate (-10°C), sec-butylacrylate (-26°C), Thoxypolyethylene glycol monomethacrylate (n=2) (-20°C), hexadecyl acrylate (35°C), etc. can be mentioned. In addition, in parentheses, Tg (°C) when used as a homopolymer is indicated.

Additionally, methoxypolyethylene glycol monomethacrylate (n=2) is a compound with the following structure.

[Formula 14]

Resin (A) may contain only one type of repeating unit (a1), or may contain two or more types.

In the resin (A), the content of the repeating unit (a1) (if there are multiple repeating units (a1), the total) is preferably 5 mol% or more, based on all 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 more preferable. Among them, the content of the repeating unit (a1) in the resin (A) (if there are multiple repeating units (a1), the total) is preferably 5 to 50 mol% relative to all repeating units of the resin (A). And, 5 to 40 mol% is more preferable, and 5 to 30 mol% is more preferable.

(repetition unit (a2))

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

Resin (A) may have one type of repeating unit (a2) having an acid-decomposable group, or may have two or more types in combination.

In the resin (A), the content of the repeating unit (a2) (if there are multiple repeating units (a2), the total) is preferably 20 mol% or less based on the total repeating units of the resin (A), and the pattern Since internal void suppression and etching resistance are more excellent, 15 mol% or less is more preferable. In addition, the lower limit of the content of the repeating unit (a2) is, for example, 3 mol% or more, preferably 5 mol% or more, relative to all repeating units of the resin (A).

As the acid-decomposable group, it is preferable that the polar group has a structure protected by a group (leaving group) that decomposes and leaves by the action of acid.

As polar groups, carboxy group, phenolic hydroxyl group, fluorinated alcohol group, sulfo group, sulfonamide group, sulfonyl imide group, (alkyl sulfonyl) (alkyl carbonyl) methylene group, (alkyl sulfonyl) (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 Acidic groups such as (alkylsulfonyl)methylene groups (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), and alcoholic hydroxyl groups are included.

In addition, an 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) bonded directly to an aromatic ring, and an aliphatic alcohol (e.g. For example, hexafluoroisopropanol group, etc.) are excluded. The alcoholic hydroxyl group is preferably a hydroxyl group with a pKa (acid dissociation constant) of 12 or more and 20 or less.

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

Groups preferred as acid-decomposable groups are groups in which the hydrogen atom of these groups is replaced with a group that is desorbed by the action of an acid (leaving group).

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

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

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

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, and jade group. Til group, etc. are mentioned.

The cycloalkyl groups of R ₃₆ to 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 include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, for example, adamantyl group, norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetra Cyclododecyl group, and androstanyl group, etc. can be mentioned. Additionally, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably aryl groups having 6 to 10 carbon atoms, and examples include phenyl groups, naphthyl groups, and anthryl groups.

The aralkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably aralkyl groups having 7 to 12 carbon atoms, and examples include benzyl group, phenethyl group, and naphthylmethyl group.

The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples include vinyl group, allyl group, butenyl group, and cyclohexenyl group.

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

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

·-COO- group is a repeating unit with a structure (acid-decomposable group) protected by a leaving group that is decomposed and released by the action of acid.

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

[Formula 15]

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 be combined to form a ring structure, or do not need to be formed.

Examples of the divalent linking group for T include alkylene group, arylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group, cycloalkylene group, or 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 is more preferably -CH ₂ -, -(CH ₂ ) ₂ -, or -(CH ₂ ) ₃ -. It is more preferable that T is a single bond.

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

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

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

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be straight chain or branched and may be methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group, etc. This is desirable. As carbon number of an alkyl group, 1-10 are preferable, 1-5 are more preferable, and 1-3 are still more preferable. In the alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ , some of the bonds between carbons may be double bonds.

The cycloalkyl groups of Rx ₁ , Rx ₂ and Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, or polycyclic groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. A cycloalkyl group in the ring is preferred.

The ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ includes monocyclic cycloalkane rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, and cyclooctane ring, or norbornene ring, Polycyclic cycloalkyl rings such as tetracyclodecane ring, tetracyclododecane ring, and adamantane ring are preferable. Among them, a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable. As the ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ , the structure shown below is also preferable.

[Formula 16]

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

[Formula 17]

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

In addition, the resin (A) is a repeating unit having an acid-decomposable group, and includes a group that is decomposed by the action of an acid and generates an alcoholic hydroxyl group as described in paragraphs [0363] to [0364] of U.S. Patent Application Publication No. 2016/0070167A1. It may have a repeating unit.

·Repeating unit with a structure (acid-decomposable group) where the phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of acid

The resin (A) preferably has a repeating unit having an acid-decomposable group and a structure in which the phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of an acid. In addition, in this specification, a phenolic hydroxyl group is a group formed by replacing the 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, and includes a benzene ring and a naphthalene ring.

Examples of the leaving group that decomposes and leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).

Equation (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), it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups.

Among them, it is more preferable that Rx ₁ to Rx ₃ are each independently repeating units representing a linear or branched alkyl group, and Rx ₁ to Rx ₃ are each independently repeating units representing a linear alkyl group. It is more desirable.

Two of Rx ₁ to Rx ₃ may be combined to form a monocyclic or polycyclic ring.

The alkyl group for Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl.

The cycloalkyl groups of Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, or polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. desirable.

Cycloalkyl groups formed by combining two of Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, or norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Polycyclic cycloalkyl groups such as these are preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.

In the cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. .

For the groups represented by formulas (Y1) and (Y2), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are preferably combined to form the above-mentioned cycloalkyl group.

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

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

As a repeating unit having a structure (acid-decomposable group) protected by a leaving group in which the phenolic hydroxyl group decomposes and desorbs under the action of acid, the hydrogen atom in the phenolic hydroxyl group is protected by a group represented by formulas (Y1) to (Y4). It is desirable to have a structured structure.

As a repeating unit having a structure (acid-decomposable group) in which the phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of an acid, a repeating unit represented by the following general formula (AII) is preferable.

[Formula 18]

In 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 combined with 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 a (n+1) valent aromatic hydrocarbon group, and when combined with R ₆₂ to form a ring, it represents a (n+2) valent aromatic hydrocarbon group.

When _n≥2 , Y 2 each independently represents a hydrogen atom or a group that is released by the action of an acid. However, at least one of Y ₂ represents a group that is eliminated by the action of an acid. The group desorbed by the action of acid as Y ₂ preferably has 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 an alkoxycarbonyl group (2 to 6 carbon atoms). ), etc., and those with 8 or less carbon atoms are preferable.

[Formula 19]

[Formula 20]

(Other repeat units)

Resin (A) may contain other repeating units in addition to the above-mentioned repeating units. Below, other repeating units that the resin (A) may contain are explained in detail.

(Repeating unit (a3) with a carboxyl group)

Resin (A) may further have a repeating unit (a3) having a carboxyl group in addition to the repeating unit (a1) and (a2) described above.

Resin (A) contains the repeating unit (a3), and thus has a superior dissolution rate during alkali development.

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

[Formula 21]

Resin (A) may have the repeating unit (a3) individually or in combination of two or more types.

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

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

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

By containing the repeating unit (a4), the resin (A) has a higher dissolution rate during alkali development and is also 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.

[Formula 22]

During the ceremony,

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 be combined 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 a (n+1) valent aromatic hydrocarbon group, and when combined with R ₄₂ to form a ring, it represents a (n+2) valent aromatic hydrocarbon group.

n represents an integer of 1 to 5.

For the purpose of making the repeating unit represented by general formula (I) highly polar, it is also preferable that n is an integer of 2 or more, or that X ₄ is -COO- or -CONR ₆₄ -.

The alkyl groups represented by R ₄₁ , R ₄₂ , and R ₄₃ in general formula (I) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, and hexyl group which may have a substituent. , 2-ethylhexyl group, octyl group, and dodecyl group, alkyl groups with 20 or less carbon atoms are preferable, alkyl groups with 8 or less carbon atoms are more preferable, and alkyl groups with 3 or less carbon atoms are still more preferable.

The cycloalkyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in general formula (I) may be monocyclic or polycyclic. Monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl group, cyclopentyl group, and cyclohexyl group, which may have a substituent, are preferable.

The halogen atom represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The alkyl group contained in the alkoxycarbonyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in general formula (I) is preferably the same as the alkyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ above.

Preferred substituents for each of the above groups include, for example, an alkyl group, cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen atom, alkoxy group, thioether group, Examples include an acyl group, acyloxy group, alkoxycarbonyl group, cyano group, and nitro group, and the number of carbon atoms of the substituent is preferably 8 or less.

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, an arylene group with 6 to 18 carbon atoms such as a phenylene group, tolylene group, naphthylene group, and anthracenylene group, or, for example, For example, aromatic hydrocarbons containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. Gi is preferable.

A specific example of the (n+1) valent aromatic hydrocarbon group when n is an integer of 2 or more is a group obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic hydrocarbon group. You can lift the flag appropriately.

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

Substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n+1)-valent aromatic hydrocarbon group may have include, for example, the alkyl groups represented by R ₄₁ , R ₄₂ , and R ₄₃ in general formula (I). ; Alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, and butoxy group; Aryl groups such as phenyl groups can be mentioned.

The alkyl group _for R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by Alkyl groups with 20 or less carbon atoms, such as ethyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, are preferable, and alkyl groups with 8 or less carbon atoms are more preferable.

As X ₄ , a single bond, -COO-, or -CONH- is preferable, and a single bond or -COO- is more preferable.

The divalent linking group as L ₄ is preferably an alkylene group, and the alkylene group is a methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group, which may have a substituent, and has 1 to 8 carbon atoms. An alkylene group is preferred.

As Ar ₄ , an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent is preferable, and a benzene ring group, a naphthalene ring group, or a biphenylene ring group is more preferable. Among them, it is preferable that the repeating unit represented by general formula (I) is a repeating unit derived from hydroxystyrene. That is, Ar ₄ is preferably a benzene ring group.

Hereinafter, specific examples of repeating units having a phenolic hydroxyl group will be shown, but the present invention is not limited to this. In the formula, a represents 1 or 2.

[Formula 23]

Resin (A) may have one type of repeating unit (a4) or may have two or more types in combination.

In the resin (A), the content of the repeating unit (a4) is preferably 40 mol% or more, more preferably 50 mol% or more, and further 60 mol% or more, relative to all repeating units in the resin (A). desirable. Moreover, the content of the repeating unit (a4) is preferably 85 mol% or less, and more preferably 80 mol% or less, relative to all repeating units in the resin (A).

(repetition unit (a5))

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 a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable. Among them, those in which another ring structure is condensed to a 5- to 7-membered ring lactone structure in the form of a bicyclo or spiro structure, or a 5- to 7-membered ring sultone structure in the form of a bicyclo or spiro structure. It is more preferable that the other ring structure is fused.

Resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3). It is more desirable to have repeating units. Additionally, the lactone structure or sultone structure may be directly bonded to the main chain. Preferred structures include general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1- A lactone structure represented by 21) or a sultone structure represented by the general formula (SL1-1) can be mentioned.

[Formula 24]

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

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

[Formula 25]

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 repeating number 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. When a plurality of R ₀ exists, each R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

Z represents a single bond, ether bond, ester bond, amide bond, urethane bond, or urea bond. When two or more Zs exist, each Z 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 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.

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

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

[Formula 26]

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

n represents an integer greater than or equal to 0.

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

A represents a single bond or a divalent linking group.

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

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 the repeating unit described in paragraphs [0370] to [0414] of US Patent Application Publication No. 2016/0070167A1. It is also desirable to have units.

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

Specific examples of monomers corresponding to the repeating unit represented by General Formula (III) and specific examples of monomers corresponding to the repeating unit represented by General Formula (A-1) are given below, but the present invention is limited to these specific examples. It doesn't work. The following specific examples correspond to the case where R ₇ in general formula (III) and R _A ¹ in general formula (A-1) are methyl groups, but R ₇ and R _A ¹ are hydrogen atoms, It may be optionally substituted with a rosene atom or a monovalent organic group.

[Formula 27]

In addition to the above monomers, the monomers shown below are also suitably used as raw materials for the resin (A).

[Formula 28]

Content of a repeating unit containing at least one type selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure contained in the resin (A) (at least one type 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, the total) is preferably 5 to 30 mol%, more preferably 10 to 30 mol%, and 20 to 30 mol% relative to all repeating units in the resin (A). is more preferable.

In addition to the above repeating structural units, the resin (A) further contains various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or general necessary properties of resist such as resolution, heat resistance, sensitivity, etc. You can have it.

Such repeating structural units include, but are not limited to, repeating structural units corresponding to predetermined monomers.

Examples of the predetermined monomer include one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. Compounds having these, etc. can be mentioned.

In addition, addition polymerizable unsaturated compounds copolymerizable with monomers corresponding to the various repeating structural units described above may be used.

In the resin (A), the molar ratio contained in each repeating structural unit is appropriately set in order to control various performances.

In the resin (A), all of the repeating units may be composed of (meth)acrylate-based repeating units. In this case, all of the repeating units are methacrylate-based repeating units, all of the repeating units are acrylate-based repeating units, and all of the repeating units are made up of methacrylate-based repeating units and acrylate-based repeating units. Any of these can be used, but it is preferable that the acrylate-based repeating units are 50 mol% or less relative to the total repeating units of the resin (A).

(Repeating unit with aromatic ring)

Resin (A) preferably has a repeating unit having an aromatic ring. That is, it is preferable that at least one type of repeating unit in the resin (A) is a repeating unit having an aromatic ring.

In the resin (A), the content of the repeating unit having an aromatic ring is, for example, 40 mol% or more, and 55 mol% or more, relative to all repeating units in the resin (A), because it has better etching resistance. This is preferable, and 60 mol% or more is more preferable. 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 for polymerization of resin (A))

Resin (A) can be synthesized according to a normal method (for example, radical polymerization). Common synthetic methods include, for example, (1) batch polymerization in which monomer species and an initiator are dissolved in a solvent and polymerized by heating; (2) heating by dropping a solution containing a monomer species and initiator over 1 to 10 hours; Examples include a dropping polymerization method of adding to a solvent, and among them, the dropping polymerization method (2) is preferable.

Examples of reaction solvents during polymerization include ethers such as tetrahydrofuran, 1,4-dioxane, and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate. Solvents, amides such as dimethylformamide and dimethylacetamide, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and cyclohexanone described later. A solvent that dissolves the composition of the present invention may be mentioned. As the reaction solvent during polymerization, it is particularly preferable to use the same solvent as the solvent used in the composition of the present invention. This can suppress the generation of particles during storage.

The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. In the polymerization reaction, it is preferable to use a commercially available radical initiator (for example, an azo-based initiator, peroxide, etc.) 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). .

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

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

Resin (A) may be used individually or in combination of two or more types.

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

(solids 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, it becomes easy to form a thick film pattern with a film thickness of, for example, 1 μm or more (preferably 10 μm or more). In addition, the solid content concentration refers to the mass percentage of the mass of other resist components (components that can constitute a resist film) excluding the solvent relative to the total mass of the composition of the present invention.

<Compounds that generate acids by irradiation of actinic rays or radiation (acid generators)>

[Compound represented by general formula (P-1)]

The composition of the present invention is a compound that generates acid upon irradiation of actinic rays or radiation, and includes a compound represented by the following general formula (P-1).

[Formula 29]

In the general formula (P-1),

Q ₁ represents a ring containing S ⁺ .

Ring Q ₁ is a 4-membered ring, a 5-membered ring, or a 6-membered ring. However, ring Q ₁ may form a condensed ring with another ring.

Ring Q ₁ has at least two carbon atoms as a reduction, and the reduction atom directly connected to S ⁺ is a carbon atom.

R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group. At least two of R ^P1 to R ^P5 may combine to form a ring.

Z ^- represents a non-nucleophilic anion.

In the general formula (P-1), Q ₁ represents a ring containing S ⁺ . The ring represented by Q ₁ may be an alicyclic ring (non-aromatic ring) or an aromatic ring, but it is preferable that it is a non-aromatic ring.

The ring represented by Q ₁ is a 4-membered ring, a 5-membered ring, or a 6-membered ring, and is preferably a 6-membered ring.

The ring represented by Q ₁ may form a condensed ring with another ring. The other ring may be an alicyclic ring (non-aromatic ring) or an aromatic ring, but it is preferable that it is a non-aromatic ring. The other ring is preferably a 4-membered ring, a 5-membered ring, or a 6-membered ring, and more preferably a 6-membered ring.

Ring Q ₁ may have a substituent. The substituent is not particularly limited, but examples include an alkyl group (preferably having 1 to 6 carbon atoms), an electron withdrawing group (eg, an acyl group, a sulfonate group), and the like.

Ring Q ₁ has at least two carbon atoms as a reduction, and the reduction atom directly connected to S ⁺ is a carbon atom.

It is preferable that ring Q ₁ has a hetero atom other than S ⁺ as a ring. The hetero atom referred to herein, in the case of a trivalent or higher hetero atom (for example, a nitrogen atom), includes a hydrogen atom or a hetero atom to which a substituent is bonded.

Hetero atoms other than S ⁺ include oxygen atom, nitrogen atom, sulfur atom, etc., and oxygen atom or nitrogen atom is preferable.

In the general formula (P-1), R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group.

The halogen atom as R ^P1 to R ^P5 is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom.

The alkyl groups as R ^P1 to R ^P5 may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 6. Examples of the alkyl group include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, and t-butyl group. The alkyl group may have a substituent, and the substituent is not particularly limited, and examples include a halogen atom.

The aryl group as R ^P1 to R ^P5 preferably has 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group. The aryl group may have a substituent.

The heteroaryl group as R ^P1 to R ^P5 is not particularly limited, but is preferably an aromatic heterocyclic group containing at least one of a sulfur atom, a nitrogen atom, and an oxygen atom as a hetero atom for reduction. The heteroaryl group may have a substituent.

The alkoxy groups as R ^P1 to R ^P5 may be linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. Examples of the alkoxy group include methoxy group, ethoxy group, and tert-butoxy group. The alkoxy group may have a substituent, and the substituent is not particularly limited, but examples include an alkoxy group (for example, an alkoxy group with 1 to 6 carbon atoms) or a cycloalkyl group (for example, a cycloalkyl group with 5 to 10 carbon atoms). You can.

At least one of R ^P1 to R ^P5 preferably represents a hydroxyl group, a halogen atom, an alkyl group, or an alkoxy group, more preferably represents a hydroxyl group, an alkyl group, or an alkoxy group, and still more preferably represents an alkoxy group.

At least two of R ^P1 to R ^P5 may combine to form a ring. When forming a ring, it is preferable that two adjacent R ^P1 to R ^P5 combine to form a ring. The ring formed may be an aliphatic ring or an aromatic ring. Moreover, the ring formed may be a hydrocarbon ring or a hetero ring.

In the general formula (P-1), Z ^- represents a non-nucleophilic anion.

Z ^- is not particularly limited, but is preferably an anion represented by any of the following general formulas (Z1) to (Z4).

[Formula 30]

In general formula (Z1), R ^Z1 represents an alkyl group.

[Formula 31]

In general formula (Z2),

Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Multiple Xfs may be the same or different.

R ^Z2 and R ^Z3 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. When there are multiple R ^Z2 and R ^Z3 , each may be the same or different.

L ^Z1 represents a divalent linking group, and when two or more L ^Z1s exist, they may be the same or different.

A ^Z1 represents an organic group containing a cyclic structure.

x represents an integer from 1 to 20, and y represents an integer from 0 to 10. z represents an integer from 0 to 10.

[Formula 32]

In general formulas (Z3) and (Z4), Rb ₃ to Rb ₇ each independently represent an alkyl group, a cycloalkyl group, or an aryl group. Rb ₃ and Rb ₄ may combine to form a ring structure. Rb ₅ and Rb ₆ may combine to form a ring structure.

In general formula (Z1), R ^Z1 represents an alkyl group and may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 6. Examples of the alkyl group include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, and t-butyl group. The alkyl group may have a substituent, and the substituent is not particularly limited. Examples of the alkyl group include a halogen atom, and a fluorine atom is preferred.

In general formula (Z2), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Multiple Xfs may be the same or different. The number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Moreover, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.

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 ^Z2 and R ^Z3 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group.

The alkyl groups represented by R ^Z2 and R ^Z3 may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkyl group include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, and t-butyl group. The alkyl group may have a substituent, and the substituent is not particularly limited. Examples of the alkyl group include a halogen atom, and a fluorine atom is preferred. The preferred range when the alkyl group represents an alkyl group substituted with at least one fluorine atom is the same as that described for Xf above.

L ^Z1 represents a divalent linking group.

As a divalent linking group, for example -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 2 combining a plurality of these. A linking group, etc. can be mentioned. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkyl A lene group- or -NHCO-alkylene group- is preferable, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene group-, or -OCO-alkylene group- are more preferable.

A ^Z1 represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable.

Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups.

The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl group, cyclohexyl group, and cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Among them, alicyclic groups having a bulky structure of 7 or more carbon atoms, such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group, are preferable.

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

The heterocyclic group may be monocyclic or polycyclic. The polycyclic type is more capable of suppressing acid diffusion. Additionally, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of heterocyclic rings having aromaticity include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocycles that do not have aromaticity include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the above-mentioned resin. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.

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

As an anion represented by general formula (Z2), SO ₃ ^- -CF ₂ -CH ₂ -OCO-(L ^Z1 )q'-A ^Z1 , SO ₃ ^- -CF ₂ -CHF-CH ₂ -OCO-(L ^Z1 ) q'-A ^Z1 , SO ₃ ^- -CF ₂ -COO-(L ^Z1 )q'-A ^Z1 , SO ₃ ^- -CF ₂ -CF ₂ -CH ₂ -CH ₂ -(L ^Z1 )zA ^Z1 , SO ₃ ^- -CF ₂ -CH(CF ₃ )-OCO-(L ^Z1 )q'-A ^Z1 is preferred. Here, L ^Z1 , z and A ^Z1 are each the same as those in general formula (Z2). q' represents an integer from 0 to 10.

In general formulas (Z3) and (Z4), Rb ₃ to Rb ₇ each independently represent an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group may be either linear or branched, and preferably has 1 to 12 carbon atoms. The cycloalkyl group may be monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms. The aryl group preferably has 6 to 14 carbon atoms.

Rb ₃ and Rb ₄ may combine to form a ring structure. Rb ₅ and Rb ₆ may combine to form a ring structure.

Specific examples of Z ^- are shown below, but are not limited to these.

[Formula 33]

[Formula 34]

The compound represented by general formula (P-1) is preferably a compound represented by the following general formula (P-2).

[Formula 35]

In the general formula (P-2),

R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group. At least two of R ^P1 to R ^P5 may combine to form a ring.

R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent.

m1 and m2 each independently represent 1 or 2.

When there are multiple R ^P6 to R ^P9 , they may be the same or different.

When m1 represents 2, two R ^P6 may combine to form a ring.

When m2 represents 2, two R ^P8s may combine to form a ring.

M ₁ represents a heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.

Z ^- represents a non-nucleophilic anion.

In the general formula (P-2), R ^P1 to R ^P5 and Z ^- have the same meaning as R ^P1 to R ^P5 and Z ^- in the general formula (P-1), respectively, and their preferred ranges are the same.

In the general formula (P-2), R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent. The substituent is not particularly limited, but examples include an alkyl group (preferably having 1 to 6 carbon atoms).

m1 and m2 each independently represent 1 or 2, and preferably represent 2.

When there are multiple R ^P6 to R ^P9 , they may be the same or different.

When m1 represents 2, two R ^P6 may combine to form a ring. The ring formed may be an alicyclic ring (non-aromatic ring) or an aromatic ring, but it is preferable that it is a non-aromatic ring. The ring formed is preferably a 4-membered ring, 5-membered ring, or 6-membered ring, and more preferably a 6-membered ring.

When m2 represents 2, two R ^P8s may combine to form a ring. The ring formed may be an alicyclic ring (non-aromatic ring) or an aromatic ring, but it is preferable that it is a non-aromatic ring. The ring formed is preferably a 4-membered ring, 5-membered ring, or 6-membered ring, and more preferably a 6-membered ring.

In the general formula (P-2), M ₁ represents a heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent. M ₁ preferably represents a hetero atom.

When M ₁ represents a hetero atom, the hetero atom is preferably an oxygen atom, a nitrogen atom, or a sulfur atom, and an oxygen atom or a nitrogen atom is more preferable. If the hetero atom can have a substituent, it may have a substituent. For example, when the hetero atom is a nitrogen atom, the substituent is preferably a group that reduces the basicity of the nitrogen atom, and examples include electron-withdrawing groups such as an acyl group and a sulfonate group. As an acyl group, an acyl group with 1 to 10 carbon atoms is preferable, and an acyl group with 1 to 5 carbon atoms is more preferable. As the sulfonate group, a sulfonate group with 1 to 10 carbon atoms is preferable, and a sulfonate group with 1 to 5 carbon atoms is more preferable.

The compound represented by general formula (P-1) is preferably a compound represented by the following general formula (P-3).

[Formula 36]

In the general formula (P-3),

R ^P1 , R ^P2 , R ^P4 , and R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group.

R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent.

m1 and m2 each independently represent 1 or 2.

When there are multiple R ^P6 to R ^P9 , they may be the same or different.

When m1 represents 2, two R ^P6 may combine to form a ring.

When m2 represents 2, two R ^P8s may combine to form a ring.

M ₁ represents a heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.

R ^P12 represents a hydrogen atom or an alkyl group.

At least two of R ^P1 , R ^P2 , R ^P4 , R ^P5 , and R ^P12 may combine to form a ring.

Z ^- represents a non-nucleophilic anion.

In the general formula (P-3), R ^P1 , R ^P2 , R ^P4 , R ^P5 , Z ^- are respectively R ^P1 , R ^P2 , R ^P4 , R ^P5 , Z ^- in the general formula (P-1) The meaning is the same, and the preferred range is also the same.

In the general formula (P-3), R ^P6 to R ^P9 , m1, m2, M ₁ each have the same meaning as R ^P6 to R ^P9 , m1, m2, M ₁ in the general formula (P-2), The preferred range is also the same.

In the general formula (P-3), R ^P12 represents a hydrogen atom or an alkyl group.

When R ^P12 represents an alkyl group, the alkyl group may be linear or branched, and is preferably linear. When R ^P12 represents an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 6. Examples of the alkyl group include methyl group, ethyl group, and tert-butyl group. The alkyl group may have a substituent, and the substituent is not particularly limited, but examples include an alkoxy group (for example, an alkoxy group with 1 to 6 carbon atoms) or a cycloalkyl group (for example, a cycloalkyl group with 5 to 10 carbon atoms). You can.

At least two of R ^P1 , R ^P2 , R ^P4 , R ^P5 , and R ^P12 may combine to form a ring. When forming a ring, it is preferable that two adjacent ones of R ^P1 , R ^P2 , R ^P4 , R ^P5 , and R ^P12 combine to form a ring. The ring formed may be an aliphatic ring or an aromatic ring. Moreover, the ring formed may be a hydrocarbon ring or a hetero ring.

The compound represented by general formula (P-1) is particularly preferably a compound represented by the following general formula (P-4) or (P-5).

[Formula 37]

[Formula 38]

In the general formulas (P-4) and (P-5),

R ^P1 , R ^P2 , R ^P4 , and R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group.

R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent.

R ^P6 to R ^P9 that exist in plural may be the same or different.

Two R ^P6s may combine to form a ring.

Two R ^P8s may combine to form a ring.

M ₁ represents a heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.

R ^P12 represents a hydrogen atom or a substituent.

At least two of R ^P1 , R ^P2 , R ^P4 , R ^P5 , and R ^P12 may combine to form a ring.

Z ^- represents a non-nucleophilic anion.

In the general formula (P-5), R ^P13 represents a hydrogen atom or a substituent.

In the general formulas (P-4) and (P-5), R ^P1 , R ^P2 , R ^P4 , R ^P5 , Z ^- are respectively R ^P1 , R ^P2 , R ^P4 in the general formula (P-1), R has the same meaning as ^P5 and Z ^- , and the preferred range is also the same.

In the general formulas (P-4) and (P-5), R ^P6 to R ^P9 each have the same meaning as R ^P6 to R ^P9 in the general formula (P-2), and their preferred ranges are also the same.

In the general formulas (P-4) and (P-5), R ^P12 has the same meaning as R ^P12 in the general formula (P-3), and the preferred range is also the same.

In the general formula (P-5), R ^P13 represents a hydrogen atom or a substituent.

When R ^P13 represents a substituent, the substituent is not particularly limited, but a group that reduces the basicity of the nitrogen atom is preferable, and examples include electron-withdrawing groups such as an acyl group and a sulfonate group. As an acyl group, an acyl group with 1 to 10 carbon atoms is preferable, and an acyl group with 1 to 5 carbon atoms is more preferable. As the sulfonate group, a sulfonate group with 1 to 10 carbon atoms is preferable, and a sulfonate group with 1 to 5 carbon atoms is more preferable.

Specific examples of the compound represented by general formula (P-1) are shown below, but are not limited to these.

[Formula 39]

[Formula 40]

[Formula 41]

The compound represented by general formula (P-1) can be synthesized by a known method (for example, the method described in Japanese Patent Application Publication No. 2014-199389).

The molecular weight of the compound represented by general formula (P-1) is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.

The compound represented by general formula (P-1) may be used individually, or two or more types may be used in combination.

In the composition of the present invention, the content of the compound represented by general formula (P-1) (sum if multiple types exist) is preferably 0.1 to 35% by mass, based on the total solid content of the composition, and is preferably 0.5 to 0.5% by mass. 25 mass% is more preferable, 1-20 mass% is more preferable, and 1-15 mass% is especially preferable.

[Photoacid generators other than compounds represented by general formula (P-1)]

The composition of the present invention is a compound that generates an acid upon irradiation of actinic light or radiation, and in addition to the compound represented by the general formula (P-1), a photoacid generator other than the compound represented by the general formula (P-1) is used. You may include more.

Examples of photo acid generators other than compounds represented by general formula (P-1) include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, Examples include diazodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.

As photoacid generators other than the compounds represented by the general formula (P-1), known compounds that generate acids when irradiated with actinic light or radiation can be appropriately selected and used individually or as a mixture thereof. For example, paragraphs [0125] to [0319] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0086] to [0094] of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/0237190A1. Known compounds disclosed in paragraphs [0323] to [0402] can be suitably used.

As photoacid generators other than compounds represented by general formula (P-1), for example, compounds represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) are preferable.

[Formula 42]

In the general formula (ZI),

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

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

Additionally, two of R ₂₀₁ to R ₂₀₃ may be combined 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. Groups formed by combining two of R ₂₀₁ to R ₂₀₃ include alkylene groups (for example, butylene groups and pentylene groups) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

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

Suitable embodiments of the cation in general formula (ZI) include compound (ZI-1), compound (ZI-2), compound (compound (ZI-3)) described later, and general formula (ZI-3). The corresponding group in the compound represented by the formula (ZI-4) (compound (ZI-4)) can be mentioned.

In addition, the photoacid generator other than the compound represented by general formula (P-1) may be a compound having a plurality of structures represented by general formula (ZI). For example, at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by general formula (ZI) represent a single bond or a linking group. It may be a compound having an intervening bond structure.

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 the general formula (ZI) is an aryl group, that is, a compound with arylsulfonium as a cation.

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

Examples of arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

As an aryl group contained in an arylsulfonium compound, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When an 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 needed is preferably a linear alkyl group with 1 to 15 carbon atoms, a branched alkyl group with 3 to 15 carbon atoms, or a cycloalkyl group with 3 to 15 carbon atoms, for example, a methyl group. , ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, and cyclohexyl group.

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

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

Compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represent an organic group without an 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, a 2-oxocycloalkyl group, or an alkoxy group. A carbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group for R ₂₀₁ to R ₂₀₃ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, and phene group). tyl group), and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group).

R ₂₀₁ to R ₂₀₃ may be further substituted by 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, compound (ZI-3) will be described.

[Formula 43]

In general formula (ZI-3), M represents an alkyl group, a cycloalkyl group, or an aryl group, and when it has a ring structure, the ring structure includes an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double. It may contain at least one type of 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. Additionally, at least two selected from M, R _6c and R _7c may be combined to form a ring structure, and the ring structure may contain a carbon-carbon double bond. Z ^- represents an anion.

In general formula (ZI-3), the alkyl group and cycloalkyl group represented by M include a straight-chain alkyl group with 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), and a linear alkyl group with 3 to 15 carbon atoms (preferably 3 to 10 carbon atoms). A branched alkyl group or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms) is preferable, and specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, and t-butyl group. , cyclopropyl group, cyclobutyl group, and cyclohexyl group, and norbornyl group.

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

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

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

The alkyl group, cycloalkyl group, and aryl group represented by R _6c and R _7c include the same as M described above, and their preferred embodiments are also the same. Additionally, 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 cycloalkyl group represented by R _x and R _y include the same ones as M described above, and their preferred embodiments are also the same.

As the alkenyl group represented by R _x and R _y , an allyl group or a vinyl group is preferable.

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

Examples of the 2-oxoalkyl group represented _{by R} Til group, etc. are mentioned.

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). Additionally, R _x and R _y may combine to form a ring.

The ring structure formed by linking R _x and R _y may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.

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

The above compound (ZI-3) is particularly preferably compound (ZI-3A).

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

[Formula 44]

In the general formula (ZI-3A),

R _1c to R _5c are each independently 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, or a hydroxyl group. , represents a nitro group, an alkylthio group, or an arylthio group.

R _6c and R _7c have the same meaning as R _6c and R _7c in the general formula (ZI-3) described above, and their preferred embodiments are also the same.

R _x and R _y have the same meaning as R _x and R _y in the general formula (ZI-3) described above, and their preferred embodiments are also the same.

_Any two or more of R _1c to R _{5c ,} R -May contain a carbon double bond. Additionally, R _5c and R _6c , R _5c and R _x may each combine to form a ring structure, and this ring structure may each independently contain a carbon-carbon double bond. Additionally, R _6c and R _7c may each be combined to form a ring structure.

Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring structure include a 3- to 10-membered ring, a 4- to 8-membered ring is preferable, and a 5- or 6-membered ring is more preferable.

Groups 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 butylene groups and pentylene groups.

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 methylene group and ethylene group.

Zc ^- represents an anion.

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

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

[Formula 45]

In the general formula (ZI-4),

l represents an integer from 0 to 2.

r represents an integer from 0 to 8.

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

When present in plural, R ₁₄ 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 an alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton. indicates. 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 be bonded to each other to form a ring.

When two R ₁₅ are bonded to each other to form a ring, hetero atoms such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. In one aspect, two R ₁₅ are alkylene groups, and it is preferable that they combine with each other to form a ring structure.

Z ^- represents an anion.

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

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

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

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

The alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ include a straight-chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, and pentyl group), or Cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) are preferred.

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

Z ^- represents an anion.

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

[Formula 46]

In general formula (3),

o represents an integer of 1 to 3. p represents an integer from 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 number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Moreover, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.

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 two or more R ₄ and R ₅ exist, R ₄ and R ₅ may be the same or different, respectively.

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 hydrogen atoms.

Specific examples and suitable aspects of the alkyl group substituted with at least one fluorine atom are the same as those of Xf in General Formula (3).

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

As a divalent linking group, for example -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 2 combining a plurality of these. A linking group, etc. can be mentioned. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkyl A lene group- or -NHCO-alkylene group- is preferable, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene group-, or -OCO-alkylene group- are more preferable.

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

Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups.

The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl group, cyclohexyl group, and cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Among them, alicyclic groups having a bulky structure of 7 or more carbon atoms, such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group, are preferable.

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

The heterocyclic group may be monocyclic or polycyclic. The polycyclic type is more capable of suppressing acid diffusion. Additionally, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of heterocyclic rings having aromaticity include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocycles that do not have aromaticity include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the above-mentioned resin. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.

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

As an anion represented by general formula (3), 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)qW, SO ₃ ^- -CF ₂ -CH(CF ₃ )-OCO-(L)q'-W is preferred. Here, L, q and W are the same as general formula (3). q' represents an integer from 0 to 10.

In one aspect, Z ^- in general formula (ZI), Z ^- in general formula (ZII), Z ^- in general formula (ZI-3), and As Zc ^- and Z ^- in general formula (ZI-4), an anion represented by general formula (4) below is also preferable.

[Formula 47]

In general formula (4),

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

X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. It is preferable that ^at least one of X ^B3 and X ^B4 is a fluorine atom or a monovalent organic group having a fluorine atom, and it is more preferable that both X ^B3 and It is more preferable that both X ^B3 and X ^B4 are alkyl groups substituted with fluorine atoms.

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

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

Z ^- in general formula (ZI), Z - in general formula (ZII), Z ^{- in} general formula (ZI-3), Zc ^- in general formula (ZI-3A), and general As Z ^- in the formula (ZI-4), an aromatic sulfonic acid anion represented by the general formula (SA1) below is also preferable.

[Formula 48]

In equation (SA1),

Ar represents an aryl group and may further have a substituent other than a sulfonic acid anion and -(D-B) group. Examples of the substituent that may be further included include a fluorine atom and a hydroxyl group.

n represents an integer of 0 or more. As n, 1 to 4 are preferable, 2 to 3 are more preferable, and 3 is more preferable.

D represents a single bond or a divalent linking group. Examples of the divalent linking group include ether group, thioether group, carbonyl group, sulfoxide group, sulfone group, sulfonic acid ester group, ester group, and groups consisting of a combination of two or more of these groups.

B represents a hydrocarbon group.

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

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

[Formula 49]

Anion Z - in general formula (ZI), general formula (ZII), Z ^- in general formula (ZI-3), ^{Zc -} in general formula (ZI-3A), and general formula (ZI- Preferred examples of Z ^- in 4) are the same as Z ^- in the compound represented by general formula (P-1).

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

Photoacid generators other than the compounds represented by general formula (P-1) may be in the form of low-molecular-weight compounds or may be in the form introduced into a part of the polymer. Additionally, a form of a low molecular compound and a form introduced into a part of a polymer may be used in combination.

It is preferable that the photoacid generator other than the compound represented by general formula (P-1) is in the form of a low molecular weight compound.

When the photo acid generator other than the compound represented by general formula (P-1) is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

When a photoacid generator other than the compound represented by general formula (P-1) is introduced into a part of the polymer, it may be introduced into a part of the above-mentioned resin (A), or may be introduced into a resin different from resin (A). .

Photoacid generators other than the compound represented by general formula (P-1) may be used individually or in combination of two or more types.

When the composition of the present invention contains a photoacid generator other than the compound represented by the general formula (P-1), the content of the photoacid generator other than the compound represented by the general formula (P-1) (if multiple types are present, Total) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, more preferably 1 to 20% by mass, and especially preferably 1 to 15% by mass, based on the total solid content of the composition. do.

As a photoacid generator other than the compound represented by the general formula (P-1), when it contains a compound represented by the general formula (ZI-3) or (ZI-4), the general formula (P-1) contained in the composition is The content of photoacid generators other than the compounds represented by (the total when multiple types exist) is preferably 1 to 35% by mass, and more preferably 1 to 30% by mass, based on the total solid content of the composition.

<Acid diffusion control agent>

The composition of the present invention preferably contains an acid diffusion control agent. The acid diffusion control agent acts as a quencher that traps acid generated from the acid-acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to the excess acid generated. For example, basic compounds (DA), basic compounds whose basicity decreases or disappears upon irradiation of actinic light or radiation (DB), onium salts (DC) which are relatively weak acids to acid generators, and which have a nitrogen atom. , a low-molecular-weight compound (DD) having a group that is released by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation portion, etc. can be used as an acid diffusion control agent. In the composition of the present invention, known acid diffusion control agents can be appropriately used. For example, paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0095] to [0187] of US Patent Application Publication No. 2015/0004544A1, and paragraphs of US Patent Application Publication No. 2016/0237190A1. Known compounds disclosed in paragraphs [0403] to [0423] and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as an acid diffusion controller.

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

[Formula 50]

Among 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 (carbon number 6~20). R ²⁰¹ and R ²⁰² may be combined with each other to form a ring.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

The alkyl groups in general formulas (A) and (E) may have a substituent or may be unsubstituted.

Regarding the above alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group with 1 to 20 carbon atoms, a hydroxyalkyl group with 1 to 20 carbon atoms, or a cyanoalkyl group with 1 to 20 carbon atoms.

The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, or piperidine, and has an imidazole structure, a diazabicyclo structure, Compounds having an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having a hydroxyl group and/or an ether bond, or aniline derivatives having a hydroxyl group and/or an ether bond, etc. It is more desirable.

A basic compound (DB) (hereinafter also referred to as “compound (DB)”) whose basicity decreases or disappears when irradiated with actinic rays or radiation has a proton acceptor functional group and is irradiated with actinic rays or radiation. It is a compound that decomposes and its proton acceptor property decreases, disappears, or changes from proton acceptor property to acidic.

A proton acceptor functional group is a functional group that has a group or electron that can electrostatically interact with a proton, for example, a functional group that has a macrocyclic structure such as a cyclic polyether, or a lone pair that does not contribute to π conjugation. It refers to a functional group having a nitrogen atom. A nitrogen atom having a lone pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

[Formula 51]

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

Compound (DB) is decomposed by irradiation of actinic light or radiation, and the proton acceptor property decreases or disappears, or a compound that changes from proton acceptor property to acidic is generated. Here, the decrease or loss of proton acceptor property, or the change from proton acceptor property to acidity, refers to a change in proton acceptor property due to the addition of a proton to a proton acceptor functional group, and specifically, the proton acceptor property. This means that when a proton adduct is generated from a compound having a functional group (DB) and a proton, the equilibrium constant in the chemical equilibrium decreases.

Proton acceptor property can be confirmed by measuring pH.

The acid dissociation constant pKa of the compound generated when the compound (DB) is decomposed by irradiation of actinic light or radiation preferably satisfies pKa<-1, and more preferably satisfies -13<pKa<-1, It is more preferable to satisfy -13<pKa<-3.

The acid dissociation constant pKa refers to the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in the Chemical Manual (II) (Revised 4th edition, 1993, Japan Chemical Society edition, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the greater the acid strength. The acid dissociation constant pKa in an aqueous solution can be specifically measured by measuring the acid dissociation constant at 25°C using an infinitely diluted aqueous solution. Alternatively, using software package 1 below, values based on Hammett's substituent constants and a database of known literature values can be obtained by calculation. All pKa values described in this specification represent values obtained by calculation using this software package.

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

In the composition of the present invention, onium salt (DC), which is a relatively weak acid compared to the photoacid generator, can be used as an acid diffusion controller.

When a mixture of a photoacid generator and an onium salt that generates an acid that is a relatively weak acid relative to the acid generated from the photoacid generator is used, the acid generated from the photoacid generator by irradiation with actinic rays or radiation produces unreacted weak acid anions. When it collides with an onium salt with a strong acid anion, a weak acid is released through salt exchange to generate an onium salt with a strong acid anion. In this process, the strong acid is exchanged for a weak acid with a lower catalytic ability, so the acid appears to be deactivated and acid diffusion can be controlled.

As onium salts that are relatively weak acids to photoacid generators, compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.

[Formula 52]

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 is a hydrocarbon containing a fluorine atom. group, and M ⁺ each independently represents an ammonium cation, a sulfonium cation, or an iodonium cation.

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

The number of carbon atoms of the hydrocarbon group represented by Z ^2c is preferably 1 to 30.

The hydrocarbon group represented by Z ^2c may have a substituent. However, it is preferable that the hydrocarbon group represented by Z ^2c does not have a fluorine atom substituted on the carbon atom adjacent to S.

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

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

Onium salt (DC), which is a relatively weak acid relative to photoacid generators, is a compound (hereinafter referred to as "compound (DCA) )" can also be used.

As the compound (DCA), a compound represented by any of the following general formulas (C-1) to (C-3) is preferable.

[Formula 53]

In 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 single bond connecting the cation site and the anion site.

-X ^- represents an anion moiety selected from -COO ^- , -SO ₃ ^- , -SO ₂ ^- , and -N ^- -R ₄ . R ₄ is, at the connection site with the adjacent N atom, 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

R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be combined with each other to form a ring structure. Moreover, in general formula (C-3), two of R ₁ to R ₃ together represent one divalent substituent, and may be bonded to the N atom by a double bond.

Substituents having 1 or more carbon atoms for R ₁ to R ₃ include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylaminocarbonyl group, and Arylaminocarbonyl group, etc. can be mentioned. Preferably, it is an alkyl group, cycloalkyl group, or aryl group.

L ₁ as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two or more types thereof. Groups formed by combination, etc. can be mentioned. 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 types thereof.

The low-molecular-weight compound (DD) (hereinafter also referred to as “compound (DD)”), which has a nitrogen atom and a group that is released by the action of an acid, is an amine derivative that has a group on the nitrogen atom that is released by the action of an acid. desirable.

As the group that is released by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group is preferable, and a carbamate group or a hemiaminal ether group is preferable. It is more desirable.

The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.

Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group is represented by the following general formula (d-1).

[Formula 54]

In general formula (d-1),

R _b is each independently a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), or an aralkyl group (preferably having 3 to 30 carbon atoms). Typically, it represents a carbon number (1 to 10 carbon atoms) or an alkoxyalkyl group (preferably a carbon number of 1 to 10). R _b may be bonded to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _b are each independently a functional group such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, and oxo group, and alkoxy group. It may be substituted with a group or a halogen atom. The same applies to the alkoxyalkyl group represented by R _b .

As R _b , a linear or branched alkyl group, cycloalkyl group, or aryl group is preferable, and a linear or branched alkyl group or cycloalkyl group is more preferable.

Examples of the ring formed by linking two R _b to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.

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

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

[Formula 55]

In general formula (6),

l represents an integer from 0 to 2, m represents an integer from 1 to 3, and satisfies l+m=3.

R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two R _a 's may be the same or different, and the two R _a 's may be connected to each other to form a heterocycle with the nitrogen atom in the formula. This heterocycle may contain heteroatoms other than the nitrogen atom in the formula.

R _b has the same meaning as R _b in the above general 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 R _a are each independently groups that may be substituted by the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R _b , and are described above. It may be substituted with the same group as the group.

Specific examples of the alkyl _group , cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) for R a include the same groups as the specific examples described above for R _b .

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 moiety is preferably an amino group, and more preferably an aliphatic amino group. It is more preferable that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Also, from the viewpoint of improving basicity, it is preferable that no electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is 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. 2015/0309408A1.

Preferred examples of acid diffusion control agents are shown below.

[Formula 56]

[Formula 57]

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

The content of the acid diffusion controller in the composition of the present invention (sum if multiple types are present) is preferably 0.05 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content of the composition. .

<Hydrophobic resin>

The composition of the present invention may contain a hydrophobic resin. Moreover, it is preferable that the hydrophobic resin is a resin different from resin (A).

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

The hydrophobic resin is preferably designed to be distributed on the surface of the resist film, but unlike the surfactant, it does not necessarily have to have a hydrophilic group in the molecule and does not have to contribute to uniform mixing of polar/non-polar substances.

The hydrophobic resin is a repeat having at least one type 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 localization to the membrane surface layer. It is preferable that it is a resin having a unit. 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 the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin contains a fluorine atom, the partial structure having a fluorine atom is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

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

(x) perinatal period

(y) A group that is decomposed by the action of an alkaline developer and increases its solubility in the alkaline developer (hereinafter also referred to as a polarity converter)

(z) Group decomposed by the action of acid

Examples of the acid group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkyl sulfonyl) (alkyl carbonyl) methylene group, (alkyl sulfonyl) (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 group. As the acid group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonimide group, or a bis(alkylcarbonyl)methylene group is preferable.

Examples of the group (y) that decomposes under the action of an alkaline developer and increases its solubility in the alkaline developer include lactone group, carboxylic acid ester group (-COO-), and acid anhydride group (-C(O)OC(O) -), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonic acid ester group (-OC(O)O-), sulfuric acid ester group (-OSO ₂ O-), and sulfonic acid ester. group (-SO ₂ O-), etc., and lactone group or carboxylic acid ester group (-COO-) is preferable. Examples of repeating units containing these groups include repeating units in which these groups are directly bonded to the main chain of the resin, and examples include repeating units made of acrylic acid ester and methacrylic acid ester. In this repeating unit, these groups may be bonded to the main chain of the resin through a linking group. Alternatively, this repeating unit may be introduced into the terminal of the resin by using a polymerization initiator or chain transfer agent having these groups during polymerization. Examples of the repeating unit having a lactone group include those identical to the repeating unit having the lactone structure described above in the section on Resin (A).

The content of the repeating unit having the group (y), which is decomposed by the action of the alkaline developer and increases its solubility in the alkaline developer, is preferably 1 to 100 mol%, and 3 to 98 mol%, based on the total repeating units in the hydrophobic resin. % is more preferable, and 5 to 95 mol% is more preferable.

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

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

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

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

The total content of the remaining 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. Moreover, the dispersion degree (Mw/Mn) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.

As the hydrophobic resin, known resins 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. 2016/0274458A1 are suitable as hydrophobic resins. It can be used easily. Additionally, 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 monomers corresponding to the repeating units constituting the hydrophobic resin are shown below.

[Formula 58]

[Formula 59]

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

<Solvent>

The composition of the present invention preferably contains a solvent. In the composition of the present invention, known resist solvents can be appropriately used. For example, paragraphs [0665] to [0670] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0210] to [0235] of US Patent Application Publication No. 2015/0004544A1, and paragraphs of US Patent Application Publication No. 2016/0237190A1. Known solvents disclosed in paragraphs [0424] to [0426], and paragraphs [0357] to [0366] of US Patent Application Publication No. 2016/0274458A1 can be suitably used. Solvents that can be used when preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactic acid ester, alkoxypropionic acid alkyl, and cyclic lactone (preferably cyclic lactone with 4 carbon atoms). to 10), monoketone compounds that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

As an organic solvent, a mixed solvent may be used in which a solvent having a hydroxyl group in the structure and a solvent not having a hydroxyl group are mixed. As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-mentioned exemplary compounds can be appropriately selected. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, and propylene glycol Colmonomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate are more preferred. Moreover, as a solvent without a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compounds which may have a ring, cyclic lactone, or alkyl acetate are preferable, and among these, propylene glycol. Lycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, and propylene glycol monomethyl Etheracetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone are more preferred. As a solvent without a hydroxyl group, propylene carbonate is also preferable. The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. A mixed solvent containing 50% by mass or more of a solvent without a hydroxyl group is preferable from the viewpoint of application uniformity. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a sole solvent of propylene glycol monomethyl ether acetate, or a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate. It's okay.

<Surfactant>

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

Because the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, especially 220 nm or less, is used, a pattern with good sensitivity and resolution and less adhesion and development defects can be obtained. As fluorine-based and/or silicone-based surfactants, the surfactants described in paragraph [0276] of US Patent Application Publication No. 2008/0248425 can be mentioned. Additionally, other surfactants other than the fluorine-based and/or silicone-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used individually, or two or more types may be used in combination. 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. On the other hand, by setting the surfactant content to 10 ppm (parts per million) or more based on the total solid content of the composition, the surface localization of the hydrophobic resin increases. As a result, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and water followability during liquid immersion exposure is improved.

<Suzy (J)>

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

The repeating unit containing the 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).

[Formula 60]

In general formula (II),

R ₂ represents a hydrogen atom, an alkyl group (preferably a methyl group) which may have a substituent, 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. Resin (J) may be used individually or in combination of two or more types. The content of resin (J) in the total solid content of the composition of the present invention is generally 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. As the resin (J), the resin disclosed in paragraphs [0142] to [0347] of US Patent Application Publication No. 2016/0282720A1 can be suitably used.

(Other additives)

The composition of the present invention may further contain an acid increasing agent, dye, plasticizer, photosensitizer, light absorber, alkali-soluble resin, dissolution inhibitor, or dissolution accelerator. As a 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 additions is preferably 2 to 10, and 2 to 6 more preferable). Specific examples of plasticizers include the following.

[Formula 61]

These plasticizers may be used individually, or two or more types may be used in combination. When the composition of the present invention contains a plasticizer, the content of the plasticizer is preferably 0.01 to 20% by mass, more preferably 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 about 50% by mass. As a solid content concentration of the composition of this invention, 25-50 mass % is especially preferable, and 30-50 mass % is still more preferable. Solid content concentration is the mass percentage of the mass of other resist components excluding the solvent relative to the total mass of the composition.

In addition, the film thickness of the actinic ray-sensitive or radiation-sensitive film (resist film) made of the composition of the present invention is preferably 1 μm or more, and for purposes such as increasing the number of processing stages and improving ion implantation resistance, it is 3 μm or more. It is preferable, 5 μm or more is more preferable, and 10 μm or more is more preferable. The upper limit is not particularly limited, but is, for example, 100 μm or less. Additionally, as described later, patterns can be formed from the composition of the present invention. The film thickness of the formed pattern is preferably 1 μm or more, and for purposes such as increasing the number of processing stages and improving ion implantation resistance, it is preferably 3 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more. The upper limit is not particularly limited, but is, for example, 100 μm or less.

The composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and then applying it onto 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. Moreover, 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 0.5 μm or less, and 0.3 μm or less. is more preferable. This filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-062667, circular filtration may be performed, or multiple types of filters may be connected in series or parallel. You may connect and perform filtration. Additionally, the composition may be filtered multiple times. Additionally, before or after filter filtration, the composition may be subjected to degassing treatment or the like.

The composition of the present invention preferably has a viscosity of 100 to 500 mPa·s. The viscosity of the composition of the present invention is more preferably 100 to 300 mPa·s because of its superior applicability. Additionally, viscosity can be measured using an E-type viscometer.

<Use>

The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change in response to irradiation of actinic rays or radiation. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit boards such as liquid crystal or thermal heads, manufacturing of mold structures for imprinting, other photofabrication processes, or flat printing plates. , or relates to an actinic ray-sensitive or radiation-sensitive resin composition used in the production of an acid-curable composition. The pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode formation process, a rewiring formation process, and MEMS (Micro Electro Mechanical Systems).

〔Pattern formation method〕

The present invention also relates to a pattern formation method using the above actinic ray-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. In addition, along with explanation of the pattern formation method, the actinic ray-sensitive or radiation-sensitive film of the present invention will also be explained.

The pattern forming method of the present invention,

(i) a step of forming a resist film (actinic ray sensitive or radiation sensitive film) on a support using the above-described actinic ray sensitive or radiation sensitive resin composition (resist film forming step),

(ii) a process of exposing the resist film (irradiating actinic light or radiation) (exposure process), and

(iii) A step of developing the exposed resist film using a developing solution (development step).

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

In the pattern formation method of the present invention, the above-described (i) resist film formation process, (ii) exposure process, and (iii) development process can be performed by generally known methods. In the pattern formation method of the present invention, the film thickness of the actinic ray-sensitive or radiation-sensitive film formed on the substrate in the (i) resist film formation step is preferably 1 μm or more, and more preferably 3 μm or more, as described above. 5μm or more is more preferable, and 10μm or more is especially preferable. The upper limit is not particularly limited, but is, for example, 100 μm or less. Additionally, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and anti-reflection film) may be formed between the resist film and the support. As the material constituting the resist underlayer film, known organic or inorganic materials can be appropriately used. A protective film (top coat) may be formed on the upper layer of the resist film. As the protective film, known materials can be appropriately used. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432, US Patents The composition for forming a protective film disclosed in Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016/157988A can be suitably used. The composition for forming a protective film preferably contains the acid diffusion control agent described above. A protective film may be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.

The support is not particularly limited, and a substrate commonly used in the manufacturing process of semiconductors such as ICs, the manufacturing process of circuit boards such as liquid crystal or thermal heads, and other lithography processes of photofabrication can be used. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ , and SiN.

The heating temperature is preferably 70 to 150°C, more preferably 70 to 130°C, more preferably 80 to 130°C, in either the (iv) pre-heating process and (v) the post-exposure heating process. ~120°C is most preferred. The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds in any of the (iv) pre-heating process and (v) post-exposure heating process. 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 light source wavelength used in the exposure process, but examples include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among these, far ultraviolet light is preferable, and its wavelength is preferably 1 to 300 nm, more preferably 100 to 300 nm, and even more preferably 200 to 300 nm. Specifically, they are KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), and electron beam, and KrF excimer laser, ArF excimer laser, EUV or electron beam. This is preferable, and the KrF excimer laser is more preferable.

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

As an alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide is usually used, but alkaline aqueous solutions such as inorganic alkalis, primary to tertiary amines, alcohol amines, and cyclic amines can also be used. Additionally, the alkaline developer may contain an appropriate amount of alcohol and/or surfactant. The alkali concentration of the alkaline developer is usually 0.1 to 20 mass%. The pH of the alkaline developer is usually 10 to 15. The development time using an alkaline developer is usually 10 to 300 seconds. The alkaline concentration, pH, and development time of the alkaline developer can be adjusted appropriately depending on the pattern to be formed.

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

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, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, Acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate can be mentioned.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and 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, butyl butanoate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate.

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

The above solvent may be mixed in plural quantities, or may be mixed with solvents other than the above or water. The moisture content of the entire developing solution is preferably less than 50% by mass, more preferably less than 20% by mass, more preferably less than 10% by mass, and it is especially preferable that it contains substantially no moisture. The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and 95 to 100% by mass, relative to the total amount of the developer. % is particularly preferred.

The organic developer may contain an appropriate amount of a known surfactant as needed.

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

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

Development methods include, for example, a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of raising the developer on the surface of the substrate by surface tension and allowing it to stand for a certain period of time (puddle method), Examples include a method of spraying the developer (spray method), or a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method).

You may combine the process of developing using an aqueous alkaline solution (alkaline developing process) and the process of developing using a developing solution containing an organic solvent (organic solvent developing process). As a result, pattern formation can be performed without dissolving only areas of intermediate exposure intensity, and thus a finer pattern can be formed.

(iii) After the development process, it is preferable to include a process of washing using a rinse solution (rinsing process).

The rinse liquid used in the rinse process after the development process using an alkaline developer can be, for example, pure water. Pure water may contain an appropriate amount of surfactant. In this case, after the developing process or rinsing process, a process of removing the developing solution or rinsing solution adhering to the pattern using a supercritical fluid may be added. Additionally, after rinsing or treatment with supercritical fluid, heat treatment may be performed to remove moisture remaining in the pattern.

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

Monohydric alcohols used in the rinse process include linear, branched, or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentane. Ol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol , and methylisobutylcarbinol. Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methylisobutylcarbinol. You can.

Each component may be mixed in plural quantities or may be used by mixing with organic solvents other than those mentioned above. The moisture content in the rinse liquid is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 3 mass% or less. By setting the moisture content to 10% by mass or less, good developing characteristics are obtained.

The rinse liquid may contain an appropriate amount of surfactant. In the rinsing process, a substrate that has been developed using an organic developer is washed using a rinsing solution containing an organic solvent. The method of cleaning treatment is not particularly limited, but examples include a method of continuously discharging a rinse solution onto a substrate rotating at a constant speed (rotation application method), a method of immersing the substrate in a tank filled with a rinse solution for a certain period of time ( Dip method), or a method of spraying a rinse solution on the surface of the substrate (spray method). Among them, it is preferable to perform cleaning treatment by a spin coating method, and to rotate the substrate at a rotation speed of 2,000 to 4,000 rpm (revolution per minute) after cleaning to remove the rinse liquid from the substrate. Additionally, it is also desirable to include a heating process (Post Bake) after the rinsing process. Through this heating process, the developer and rinse solution remaining between and inside the patterns are removed. In the heating process after the rinsing process, 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, 30 seconds to 90°C. Seconds are preferred.

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 (e.g., resist solvent, developer, rinse solution, composition for forming an anti-reflective film, or top coat forming composition, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt (parts per trillion) or less, more preferably 10 ppt or less, and substantially no content (detection limit of the measuring device). The following) are particularly preferable.

A method of removing impurities such as metals from the various materials mentioned above includes, for example, filtration using a filter. As for the filter pore diameter, the pore size is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one that has been previously washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel and used. When using multiple types of filters, filters with different pore diameters and/or materials may be used in combination. Additionally, various materials may be filtered multiple times, and the process of filtering multiple times may be a circular filtration process. As a filter, one with reduced eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Application Publication No. 2016-201426) is preferable. In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. As the adsorbent, a known adsorbent can be used, for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Application Publication No. 2016-206500). In addition, methods for reducing impurities such as metals contained in the various materials include selecting raw materials with a low metal content as raw materials constituting the various materials, performing filter filtration on the raw materials constituting the various materials, or using a device. Methods include lining the inside with Teflon (registered trademark) and performing distillation under conditions that suppress contamination as much as possible. Preferred conditions for filter filtration of raw materials constituting various materials are the same as the conditions described above.

In order to prevent the mixing of impurities, the various materials described above are stored in containers described in U.S. Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Publication No. 2015-123351), etc. It is desirable.

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

[Method for manufacturing electronic devices]

Moreover, the present invention also relates to a manufacturing method of an electronic device, including the pattern formation method described above. The electronic device manufactured by the electronic device manufacturing method of the present invention is suitable for electrical and electronic devices (e.g., home appliances, OA (Office Automation) related devices, media related devices, optical devices, and communication devices, etc.) It is mounted properly.

Example

The present invention will be described in more detail below based on examples. Materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the examples shown below.

<Suzy>

For the resin used, the structure of the repeating unit and its content (molar ratio), weight average molecular weight (Mw), and dispersion degree (Mw/Mn) are shown. In addition, the weight average molecular weight (Mw) and dispersion (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (converted to polystyrene). In addition, the content of repeating units was measured by ¹³ C-NMR (nuclear magnetic resonance).

[Formula 62]

[Formula 63]

[Formula 64]

[Formula 65]

For each resin, the content (mol%) of repeating unit (a1) derived from a monomer (monomer a1) with a glass transition temperature of 50°C or lower when converted into a homopolymer, the type of monomer a1, and the conversion of monomer a1 into a homopolymer. glass transition temperature (Tg), type of monomer corresponding to the repeating unit (a2) having an acid-decomposable group, content of the repeating unit (a2), type of monomer corresponding to the repeating unit (a3) having a carboxyl group, repetition Content of unit (a3), type of monomer corresponding to repeating unit (a4) having a phenolic hydroxyl group, content of repeating unit (a4), type of monomer corresponding to other repeating units, and content of other repeating units. is listed in Table 1. The content of each repeating unit is the molar ratio with respect to all repeating units contained in the resin.

(Method for measuring glass transition temperature of homopolymer)

The glass transition temperature of the homopolymer was taken from a catalog or literature value if available, and if not available, it was measured by differential scanning calorimetry (DSC). The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg was set to 18000, and the dispersion degree (Mw/Mn) was set to 1.7. As the DSC device, a thermal analysis DSC differential scanning calorimeter type Q1000 manufactured by TA Instrument Japan Co., Ltd. was used, and the temperature increase rate was measured at 10°C/min. In addition, the homopolymer used for measurement of Tg was synthesized by the following procedure using the corresponding monomer. In addition, the synthesis of homopolymers is performed 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 mass% of the corresponding monomer and 0.35 mass% of dimethyl 2,2'-azobisisobutyrate was added dropwise over 6 hours. After the dropwise addition was completed, the mixture was stirred at 80°C for an additional 2 hours. After the reaction solution was left to cool, it was reprecipitated with a large amount of methanol/water (mass ratio 9:1), filtered, and the obtained solid was dried to obtain a homopolymer (Mw: 18000, Mw/Mn: 1.7). The obtained homopolymer was subjected to DSC measurement. The DSC device and temperature increase rate were as described above.

[Table 1]

In addition, the glass transition temperature when the monomer (ME-1) corresponding to the other repeating units contained in resins AX-1 and AX-2 was used as a homopolymer was 54°C.

[Formula 66]

[Formula 67]

<Acid generator>

The structure of the photoacid generator used is shown below.

[Formula 68]

[Formula 69]

[Formula 70]

[Formula 71]

<Acid diffusion control agent>

The acid diffusion control agent used is shown below.

[Formula 72]

<Surfactant>

The surfactants used are shown below.

[Formula 73]

(E-2): Megapak R-41 (manufactured by DIC Corporation)

<Other additives>

Other additives used are shown below.

[Formula 74]

[Formula 75]

<Solvent>

The solvents used are shown below.

S-1: Propylene glycol monomethyl ether acetate (PGMEA)

S-2: Propylene glycol monomethyl ether (PGME)

S-3: Ethyl lactate (EL)

S-4: ethyl 3-ethoxypropionate (EEP)

S-5: 2-heptanone (MAK)

S-6: Methyl 3-methoxypropionate (MMP)

S-7: 3-methoxybutyl acetate

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

Each component shown in Table 2 was mixed to obtain the solid content concentration (mass %) shown in Table 2 to obtain a solution. Next, the obtained solution was filtered through a polyethylene filter with a pore size of 3 μm to prepare actinic ray-sensitive or radiation-sensitive resin compositions (resist compositions) res-1 to res-21 and res-1X to res-4X. . In addition, in a resist composition, solid content means all components other than the solvent.

In Table 2, the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content. In addition, Table 2 lists the content ratio (% by mass) of the solvents used relative to all solvents.

[Table 2]

〔Pattern formation and various evaluations〕

<Pattern formation>

Using spin coater ACT-8 manufactured by Tokyo Electron, the resist composition prepared above was applied on a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane, without providing an anti-reflection layer, while the substrate was stationary. Dropped. After dropping, the substrate is rotated and the rotation speed is maintained at 500 rpm for 3 seconds, then maintained at 100 rpm for 2 seconds, maintained at 500 rpm for an additional 3 seconds, and maintained at 100 rpm for another 2 seconds, and then the film thickness The set rotation speed was increased to 1200 rpm and maintained for 60 seconds. After that, heat drying was performed on a hot plate at 130°C for 60 seconds to form a positive resist film with a film thickness of 11 μm. Against this resist film, a KrF excimer laser scanner (manufactured by ASML, PAS5500/ The pattern was exposed using 850C (wavelength: 248 nm) under exposure conditions of NA = 0.60 and σ = 0.75. After irradiation, bake at 120°C for 60 seconds, immerse in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinse with pure water for 30 seconds and dry, with a space width of 5 μm and a pitch width of 25 μm. formed an isolated space pattern. The pattern exposure is exposure through a mask having a line and space pattern with a space width of 5 μm and a pitch width of 25 μm after reduced projection exposure, and the exposure amount is an isolated space with a space width of 5 μm and a pitch width of 25 μm. The optimal exposure amount (sensitivity) (mJ/cm ² ) to form a pattern was set. In determining the sensitivity, a scanning electron microscope (SEM) (9380II manufactured by Hitachi High Technologies Co., Ltd.) was used to measure the space width of the pattern. By the above procedure, a pattern was formed on the substrate.

<Performance evaluation>

Using spin coater ACT-8 manufactured by Tokyo Electron, the resist composition prepared above was applied on a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane, without providing an anti-reflection layer, while the substrate was stationary. Dropped. After dropping, the substrate is rotated and the rotation speed is maintained at 500 rpm for 3 seconds, then maintained at 100 rpm for 2 seconds, maintained at 500 rpm for an additional 3 seconds, and maintained at 100 rpm for another 2 seconds, and then the film thickness The set rotation speed was increased to 1200 rpm and maintained for 60 seconds. After that, heat drying was performed on a hot plate at 130°C for 60 seconds to form a positive resist film with a film thickness of 11 μm. A substrate (wafer) with a resist film was set in a dry etching device (U-621, manufactured by Hitachi High Technologies Co., Ltd.), and a mixture of CF ₄ , Ar, and N ₂ (gas ratio, 1:10:10) was used at a gas pressure of 4 Pa. , etching process for 30 seconds under the conditions of plasma power of 1600W and substrate bias of 1200W, and etching process for 60 seconds with O ₂ and CF ₄ mixed gas (gas ratio, 20:1) under the conditions of gas pressure of 2Pa, plasma power of 800W, and substrate bias of 0W. The etching process was continued, and the etching process was repeated six times each. The wafer after the etching treatment was fractured, and the resist cross section was observed at a magnification of 10000 using a scanning electron microscope (SEM) (S-4800, manufactured by Hitachi High Technologies Co., Ltd.). Voids (voids) in the observed resist film were counted, and each of the large voids (voids with a size of 50 nm or more) and small voids (with a size of less than 50 nm) was judged based on the following criteria.

[Number of large voids]

A: 0 (not observed at all)

B: Less than 10

C: 10 or more

[Number of small voids]

X: 0 (not observed at all)

Y: less than 10

Z: 10 or more

[Table 3]

From the results in Table 3, the resist compositions of the examples were able to suppress the generation of large voids in the resist film and also reduce small voids. In particular, in the examples, even the smallest voids less than 20 nm in size were not observed at all, or if observed, they were less than 10. Therefore, according to the resist composition of the example, the actinic ray-sensitive or radiation-sensitive resin composition can form a pattern in which large voids and small voids are unlikely to occur inside the pattern during etching, and the actinic ray-sensitive or radiation-sensitive resin composition. A resist film formed from a radiation-sensitive resin composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method of manufacturing an electronic device can be provided.

Claims (14)

An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) and a compound that generates acid upon irradiation of 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 converted 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 repeating unit (a1) is a repeating unit represented by the following general formula (1-2) or a repeating unit represented by the following general formula (1-3),
The resin (A) has a repeating unit having an aromatic ring,
An actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound that generates acid upon irradiation of actinic rays or radiation includes a compound represented by the following general formula (P-1).

In general formula (1-2), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₂ is ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethyl. It represents a group selected from pentyl group and 2-ethylhexyl group.

In general formula (1-3), R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₄ represents a non-acid-decomposable alkyl group having a carboxy group that may contain a hetero atom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group that may contain a hetero atom in the chain.
[Formula 1]

In the general formula (P-1),
Q ₁ represents a ring containing S ⁺ .
Ring Q ₁ is a 4-membered ring, a 5-membered ring, or a 6-membered ring. However, ring Q ₁ may form a condensed ring with another ring.
Ring Q ₁ has at least two carbon atoms as a reduction, and the reduction atom directly connected to S ⁺ is a carbon atom.
R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group. At least two of R ^P1 to R ^P5 may combine to form a ring.
Z ^- represents a non-nucleophilic anion. In claim 1,
An actinic ray-sensitive or radiation-sensitive resin composition wherein Q ₁ is a non-aromatic ring. In claim 1 or claim 2,
An actinic ray-sensitive or radiation-sensitive resin composition wherein Q ₁ has a hetero atom other than S ⁺ as a reduction. In claim 1 or claim 2,
An actinic ray-sensitive or radiation-sensitive resin composition wherein the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-2).
[Formula 2]

In the general formula (P-2),
R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group. At least two of R ^P1 to R ^P5 may combine to form a ring.
R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent.
m1 and m2 each independently represent 1 or 2.
When there are multiple R ^P6 to R ^P9 , they may be the same or different.
When m1 represents 2, two R ^P6 may combine to form a ring.
When m2 represents 2, two R ^P8s may combine to form a ring.
M ₁ represents a heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.
Z ^- represents a non-nucleophilic anion. In claim 1 or claim 2,
An actinic ray-sensitive or radiation-sensitive resin composition wherein the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-3).
[Formula 3]

In the general formula (P-3),
R ^P1 , R ^P2 , R ^P4 , and R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group.
R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent.
m1 and m2 each independently represent 1 or 2.
When there are multiple R ^P6 to R ^P9 , they may be the same or different.
When m1 represents 2, two R ^P6 may combine to form a ring.
When m2 represents 2, two R ^P8s may combine to form a ring.
M ₁ represents a heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.
R ^P12 represents a hydrogen atom or an alkyl group.
At least two of R ^P1 , R ^P2 , R ^P4 , R ^P5 , and R ^P12 may combine to form a ring.
Z ^- represents a non-nucleophilic anion. In claim 1 or claim 2,
An actinic ray-sensitive or radiation-sensitive resin composition wherein the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-4) or (P-5).
[Formula 4]

[Formula 5]

In the general formulas (P-4) and (P-5),
R ^P1 , R ^P2 , R ^P4 , and R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group.
R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent.
R ^P6 to R ^P9 that exist in plural may be the same or different.
Two R ^P6s may combine to form a ring.
Two R ^P8s may combine to form a ring.
R ^P12 represents a hydrogen atom or an alkyl group.
At least two of R ^P1 , R ^P2 , R ^P4 , R ^P5 , and R ^P12 may combine to form a ring.
Z ^- represents a non-nucleophilic anion.
In the general formula (P-5), R ^P13 represents a hydrogen atom or a substituent. In claim 1 or claim 2,
An actinic ray-sensitive or radiation-sensitive resin composition having a solid content concentration of 10% by mass or more. In claim 1 or claim 2,
An actinic ray-sensitive or radiation-sensitive resin composition wherein Z ^- is an anion represented by any of the following general formulas (Z1) to (Z4).
[Formula 6]

In general formula (Z1), R ^Z1 represents an alkyl group.
[Formula 7]

In general formula (Z2),
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Multiple Xfs may be the same or different.
R ^Z2 and R ^Z3 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. When there are multiple R ^Z2 and R ^Z3 , each may be the same or different.
L ^Z1 represents a divalent linking group, and when two or more L ^Z1s exist, they may be the same or different.
A ^Z1 represents an organic group containing a cyclic structure.
x represents an integer from 1 to 20, and y represents an integer from 0 to 10. z represents an integer from 0 to 10.
[Formula 8]

In general formulas (Z3) and (Z4), Rb ₃ to Rb ₇ each independently represent an alkyl group, a cycloalkyl group, or an aryl group. Rb ₃ and Rb ₄ may combine to form a ring structure. Rb ₅ and Rb ₆ may combine to form a ring structure. delete A resist film formed by the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2. (i) A process of forming an actinic ray-sensitive or radiation-sensitive film with a film thickness of 1 μm or more on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition,
(ii) a process of irradiating actinic rays or radiation with a wavelength of 200 to 300 nm to the actinic ray-sensitive or radiation-sensitive film, and
(iii) A pattern forming method comprising the step of developing the actinic ray or radiation sensitive film irradiated with actinic ray or radiation using a developer,
The actinic ray-sensitive or radiation-sensitive resin composition is an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) and a compound that generates an acid upon irradiation of 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 converted 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 repeating unit (a1) is a repeating unit represented by the following general formula (1-2) or a repeating unit represented by the following general formula (1-3),
The resin (A) has a repeating unit having an aromatic ring,
The pattern forming method wherein the compound that generates acid upon irradiation of actinic rays or radiation is an actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the following general formula (P-1).

In general formula (1-2), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₂ is ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethyl. It represents a group selected from pentyl group and 2-ethylhexyl group.

In general formula (1-3), R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₄ represents a non-acid-decomposable alkyl group having a carboxy group that may contain a hetero atom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group that may contain a hetero atom in the chain.
[Formula 9]

In the general formula (P-1),
Q ₁ represents a ring containing S ⁺ .
Ring Q ₁ is a 4-membered ring, a 5-membered ring, or a 6-membered ring. However, ring Q ₁ may form a condensed ring with another ring.
Ring Q ₁ has at least two carbon atoms as a reduction, and the reduction atom directly connected to S ⁺ is a carbon atom.
R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group. At least two of R ^P1 to R ^P5 may combine to form a ring.
Z ^- represents a non-nucleophilic anion. A method of manufacturing an electronic device comprising the pattern forming method according to claim 11. delete In claim 1 or claim 2,
The repeating unit (a1) is a repeating unit represented by the following general formula (1-2) or a repeating unit represented by the following general formula (1-3),
An actinic ray-sensitive or radiation-sensitive resin composition wherein the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-4) or (P-5).

In general formula (1-2), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₂ is ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethyl. It represents a group selected from a pentyl group, a 2-ethylhexyl group, and a monovalent alkyl group in which one or two or more of them -CH ₂ - is substituted with -O- or -O-CO-.

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


In the general formulas (P-4) and (P-5),
R ^P1 , R ^P2 , R ^P4 , and R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or an alkoxy group.
R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent.
R ^P6 to R ^P9 that exist in plural may be the same or different.
Two R ^P6s may combine to form a ring.
Two R ^P8s may combine to form a ring.
R ^P12 represents a hydrogen atom or an alkyl group.
At least two of R ^P1 , R ^P2 , R ^P4 , R ^P5 , and R ^P12 may combine to form a ring.
Z ^- represents a non-nucleophilic anion.
In the general formula (P-5), R ^P13 represents a hydrogen atom or a substituent.