KR20210032463A - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming 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 and a repeating unit having an acid-decomposable group, derived from a monomer having a glass transition temperature of 50° C. or less when used as a homopolymer, and a compound represented by General Formula (P-1) The actinic ray-sensitive or radiation-sensitive resin composition, the 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 the former It is a method of manufacturing a device.

Ring Q ₁ is a 4-6 membered ring. However, ring Q ₁ may form a condensed ring with another ring.
Ring Q ₁ has at least two carbon atoms as reduction, and the reduction atom directly connected to ^{S + is a carbon atom.} Each of R ^P1 to R ^P5 independently represents 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 forming 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 forming method, and a method of manufacturing an electronic device.

After the resist for a KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method of the resist in order to compensate for the decrease in sensitivity due to light absorption. For example, as a positive-type chemical amplification image forming method, by exposure such as excimer laser, electron beam, and extreme ultraviolet light, the photoacid generator in the exposed portion is decomposed to produce an acid, followed by baking (PEB: PostExposure Bake). An image forming method in which the generated acid is used as a reaction catalyst, an alkali-insoluble group is changed to an alkali-soluble group, and an exposed portion is removed with an alkali developer.

On the other hand, these days, miniaturization using the wavelength of the exposure light source has reached its limit, and in particular, in ion implantation process applications and NAND memory (NOT AND memory), for the purpose of increasing the capacity, three-dimensionalization of the memory layer is becoming the mainstream. . Since it is necessary to increase the number of processing stages in the vertical direction for the three-dimensionalization of the memory layer, the resist film is required to be thickened from the conventional nanoscale to the micron size.

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

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

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

Accordingly, 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 in the pattern during etching, the actinic ray-sensitive or radiation-sensitive resin It is an object to provide a resist film formed from a composition, a pattern forming method using the actinic-ray-sensitive or radiation-sensitive resin composition, and a method of manufacturing an electronic device.

The present inventors, as a result of careful examination in order to solve the above problems, showed that the actinic ray property containing a specific resin and a compound of a specific structure (a photoacid generator of a specific structure) that generates an acid by irradiation with actinic rays or radiation. Or according to a radiation-sensitive resin composition, it found what can solve the said subject, and completed this invention.

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

<1>

As an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) and a compound that generates an acid by irradiation with actinic ray or radiation,

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

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

The compound that generates an acid by irradiation with actinic ray or radiation includes a compound represented by the following general formula (P-1), an actinic ray-sensitive or radiation-sensitive resin composition.

[Formula 1]

In the general formula (P-1),

Q ₁ represents a ring containing S ^+.

Ring Q ₁ is a 4-membered ring, 5-membered ring, or 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 reduction, and the reduction atom directly connected to ^{S + is a carbon atom.}

Each of R ^P1 to R ^P5 independently represents 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 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),

Each of R ^P1 to R ^P5 independently represents 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 a ^{plurality of R P6} to R ^P9 exist respectively, they may be the same or different.

When m1 represents 2, two R ^P6 may be bonded to each other to form a ring.

When m2 represents 2, two R ^P8s may be bonded to each other to form a ring.

M ₁ represents a hetero atom 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 a ^{plurality of R P6} to R ^P9 exist respectively, they may be the same or different.

When m1 represents 2, two R ^P6 may be bonded to each other to form a ring.

When m2 represents 2, two R ^P8s may be bonded to each other to form a ring.

M ₁ represents a hetero atom 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 be} bonded to form a ring.

Z ^- represents a non-nucleophilic anion.

<6>

The actinic ray-sensitive or radiation-sensitive 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) Castle 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.

A plurality of R ^P6 to R ^P9 may be the same or different, respectively.

Two R ^P6 may be bonded to each other to form a ring.

Two R ^P8 may be bonded to each other to form a ring.

M ₁ represents a hetero atom 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 be} bonded 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 one 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),

Each of Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Multiple Xf's may be the same or different, respectively.

R ^Z2 and R ^Z3 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. ^{R Z2} and R ^Z3 in the case of a plurality of occurrences may be the same or different, respectively.

L ^Z1 represents a divalent linking group, and L ^Z1 may be the same as or different from each other in the case of a plurality of present.

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

x represents the integer of 1-20, and y represents the integer of 0-10. z represents the integer of 0-10.

[Formula 8]

In general formulas (Z3) and (Z4), Rb ₃ to Rb ₇ each independently represents an alkyl group, a cycloalkyl group, or an aryl group. Rb ₃ and Rb ₄ may be bonded to each other to form a ring structure. Rb ₅ and Rb ₆ may be bonded to each other 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 from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <9>.

<11>

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

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

(iii) A pattern formation method having a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the 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 by irradiation with actinic ray or radiation,

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

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

The compound that generates an acid by irradiation with actinic ray or radiation is an actinic ray-sensitive or radiation-sensitive resin composition comprising 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, 5-membered ring, or 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 reduction, and the reduction atom directly connected to ^{S + is a carbon atom.}

Each of R ^P1 to R ^P5 independently represents 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>

An electronic device manufacturing method including the pattern formation method according to <11>.

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

Hereinafter, the present invention will be described in detail.

The description of the constitutional requirements described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

"Active ray" or "radiation" in the present specification means, for example, a bright ray spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, And an electron beam (EB). In this specification, "light" means actinic ray or radiation. In the present specification, "exposure" refers to particles such as electron beams and ion beams, as well as exposures by the bright ray spectrum of mercury lamps, far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV, etc. typified by excimer lasers, unless otherwise specified. Also includes drawing by lines.

In this specification, "~" is used as a meaning including numerical values described before and after it as a lower limit value and an upper limit value.

In the present specification, (meth)acrylate represents at least one of acrylate and methacrylate. Moreover, (meth)acrylic acid represents at least 1 type of acrylic acid and methacrylic acid.

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

Regarding the notation of the group (atomic group) in the present specification, the notation in which substituted and unsubstituted are not described includes groups having no substituents and groups having substituents. For example, the "alkyl group" includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In addition, the "organic group" in this specification means a group containing at least one carbon atom.

In addition, in the present specification, the type of the substituent, the position of the substituent, and the number of the substituents in the case of "you may have a substituent" are not particularly limited. The number of substituents may be, for example, 1, 2, 3, or more. Examples of the substituent include a monovalent nonmetallic group excluding a hydrogen atom, and for example, it can be selected from the following substituents T.

(Substituent T)

Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; Alkoxy groups such as a methoxy group, an ethoxy group, and a 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 an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxylyl 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; Carboxy; Pom Diary; Sulfo group; Cyano group; Alkylaminocarbonyl group; Arylaminocarbonyl group; Sulfonamide group; Silyl group; Amino group; Monoalkylamino group; Dialkylamino group; And arylamino groups and combinations thereof.

[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 by irradiation with actinic rays or radiation. As an actinic-ray-sensitive or radiation-sensitive resin composition, the resin (A) is a repeating unit (a1) derived from a monomer having a glass transition temperature of 50°C or less when used as a homopolymer, and a repeating unit having an acid-decomposable group (a2), wherein the repeating unit (a1) is a non-acid-decomposable repeating unit, and the compound that generates an acid by irradiation with 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, 5-membered ring, or 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 reduction, and the reduction atom directly connected to ^{S + is a carbon atom.}

Each of R ^P1 to R ^P5 independently represents 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 alkali development may be sufficient, and the resist composition for organic solvent development may be sufficient. Among them, it is a positive resist composition, and a resist composition for alkali development is preferable.

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 not to contain a crosslinking agent.

The reason why a pattern in which large voids and small voids are unlikely to occur in the pattern can be formed by the composition of the present invention during etching, but it is estimated as follows.

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

The present inventors have used a resin (resin (A)) having a repeating unit (repeating unit (a1)) derived from a monomer having a glass transition temperature of 50° C. or less when a homopolymer is used as the acid-decomposable resin, It was examined to improve the plasticity of the. Thereby, the decomposition product of the photoacid generator can be easily removed from the inside of the pattern by volatilization, and large voids can be reduced.

However, even in the case of using the resin (A), there is room for improvement regarding the reduction of small voids.

Therefore, the inventors of the present invention considered that if the cation of the photoacid generator decomposed by exposure is highly volatile, it does not remain inside the pattern, and the generation of voids during etching is suppressed because it volatilizes before etching. And it was found that not only large voids but also small voids can be greatly reduced by using the resin (A) and the photoacid generator represented by the general formula (P-1) together. Particularly, according to the present invention, it was found that even a very small void having 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 is the present invention when the repeating unit derived from a monomer having a glass transition temperature of 50° C. or less in the case of a homopolymer is an acid-decomposable repeating unit (e.g., a repeating unit derived from tert-butyl acrylate). It is based on the inability to exert the effect of. That is, under the environment at the time of etching, the photoacid generator remaining in the pattern is decomposed to generate acid, and the deprotection reaction of the remaining acid-decomposable repeating units 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, it is considered that acrylic acid is a monomer having a glass transition temperature higher than 50°C when used as a homopolymer, so that the plasticity of the pattern cannot be improved, and the void reduction effect cannot be obtained.

<Resin (A)>

The resin (A) contained in the composition of the present invention is a repeating unit (a1) derived from a monomer having a glass transition temperature (Tg) of 50°C or less when used as a homopolymer, and a repeating unit (a2) having an acid-decomposable group. And the repeating unit (a1) is a non-acid-decomposable repeating unit.

Resin (A) is a resin (acid-decomposable resin) whose polarity is increased by decomposition by the action of an acid because it contains a repeating unit having an acid-decomposable group. That is, in the pattern formation method of the present invention described later, typically, when an alkaline developer is used as a developer, a positive pattern is suitably formed, and when an organic developer is used as a developer, a negative pattern is It is suitably formed.

(Repeat 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 a homopolymer is formed.

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

(Measurement method of glass transition temperature of homopolymer)

When there is a catalog value or a document value, the glass transition temperature of a homopolymer is taken, and when there is no, it is measured by a differential scanning calorimetry (DSC) method. The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg is set to 18000, and the degree of dispersion (Mw/Mn) is set to 1.7. As a DSC device, a thermal analysis DSC differential scanning calorimeter Q1000 type manufactured by TA Instruments Japan Co., Ltd. is used, and the temperature increase rate is measured at 10°C/min.

Further, the homopolymer used for the measurement of Tg may be synthesized by a known method using a corresponding monomer, and for example, it can be synthesized by a general dropping polymerization method or the like. 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 liquid, 125 mass parts of a PGMEA solution containing 21 mass% of corresponding monomers and 0.35 mass% of dimethyl 2,2'-azobisisobutyrate were dripped over 6 hours. After completion of dropping, it stirred at 80 degreeC for 2 hours. The reaction solution was allowed to stand to cool, then reprecipitated and filtered with a large amount of methanol/water (mass ratio 9:1), 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 apparatus and the rate of temperature increase were as described above.

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

The repeating unit (a1) is preferably 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, since it can easily volatilize the low-molecular compound remaining in the film out of the system. . In the present specification, "non-acid-decomposable" means that the photoacid generator has a property of not causing a desorption/decomposition reaction by an acid generated.

That is, "non-acid decomposable alkyl group" is more specifically, an alkyl group that does not decompose from the resin (A) by the action of an acid generated by the photoacid generator, or an alkyl group that does not decompose by the action of an acid generated by the photoacid generator Can be lifted.

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, which may contain a hetero atom in the chain, is not particularly limited, but, for example, an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms containing a hetero atom in the chain Can be lifted.

As a C2-C20 alkyl group containing a hetero atom in a chain, for example, 1 or 2 or more -CH ₂ -is, -O-, -S-, -CO-, -NR ₆ -, or these are 2 The alkyl group substituted with the divalent organic group combined above is mentioned. Said R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of the non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a hetero atom in the chain include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group , Lauryl group, stearyl group, isobutyl group, sec-butyl group, 1-ethylpentyl group and 2-ethylhexyl group, and one or two or more of these -CH ₂ -is -O- or -O And a monovalent alkyl group substituted with -CO-.

The number of carbon atoms 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 or more and 16 or less, more preferably 2 or more and 10 or less, and still more preferably 2 or more and 8 or less.

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

It is preferable that the repeating unit (a1) is 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.

Although it does not specifically limit as a halogen atom represented by R<_1> , For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

Although it does not specifically limit as an alkyl group represented by R<_1> , For example, a C1-C10 alkyl group is mentioned, Specifically, a methyl group, an ethyl group, a tert-butyl group, etc. are mentioned. Among them, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.

Although it does not specifically limit as a cycloalkyl group represented by R<_1> , For example, a C5-10 cycloalkyl group is mentioned, More specifically, a cyclohexyl group etc. are mentioned.

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

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

In addition, the repeating unit (a1) is a non-acid decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the chain, or reduction in that it can easily volatilize the low-molecular compound remaining in the film out of the system. It may be a repeating unit having a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom.

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

As the non-acid-decomposable alkyl group, either linear or branched chain may be used.

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

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

As a C2-C20 alkyl group containing a hetero atom in a chain, for example, 1 or 2 or more -CH ₂ -is, -O-, -S-, -CO-, -NR ₆ -, or these are 2 The alkyl group substituted with the divalent organic group combined above is mentioned. Said R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As carbon number of the non-acid-decomposable alkyl group which may contain a hetero atom in a chain, 2-16 are preferable, 2-10 are more preferable, and 2-8 are more preferable from a viewpoint of void suppression inside a pattern.

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

As a specific example of the repeating unit which contains a hetero atom in a chain and which has a non-acid-decomposable alkyl group which has a carboxy group, the repeating unit of the following structure is mentioned, for example.

[Formula 12]

The number of carbon atoms of the non-acid-decomposable cycloalkyl group is preferably 5 or more, and 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 from the viewpoint of the homopolymer Tg being 50°C or less. It is more preferable and it is more preferable that it is 10 or less.

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

As a C5-C20 cycloalkyl group containing a hetero atom in reduction, for example, one or two or more -CH ₂ -is, -O-, -S-, -CO-, -NR ₆ -, or these And a cycloalkyl group 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.

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

As a repeating unit having a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the chain, a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group in the reduction, or a hetero atom in the reduction, Since the effect is more excellent, among them, the repeating unit represented by the following general formula (1-3) is 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 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 reduction.

In General Formula (1-3), R ₃ has the _{same meaning as R 1} described above, and a preferred aspect is also the same.

Definitions and suitable embodiments of a non-acid-decomposable alkyl group having a hetero atom in the chain represented by R ₄ or having a carboxy group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group in the reduction Is as described above.

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

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

In addition, methoxypolyethylene glycol monomethacrylate (n=2) is a compound of the following structure.

[Formula 14]

Resin (A) may contain only 1 type, and may contain 2 or more types of repeating units (a1).

In the resin (A), the content of the repeating unit (a1) (when a plurality of repeating units (a1) are present, the total) is preferably 5 mol% or more with respect to 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 still more preferable. Among them, the content of the repeating unit (a1) in the resin (A) (when a plurality of repeating units (a1) are present, the total) is preferably 5 to 50 mol% with respect to the total repeating units of the resin (A). And 5-40 mol% is more preferable, and 5-30 mol% is more preferable.

(Repeat unit (a2))

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

Resin (A) may have the repeating unit (a2) which has an acid-decomposable group individually by 1 type, and may use 2 or more types together, and may have it.

In the resin (A), the content of the repeating unit (a2) (when a plurality of repeating units (a2) are present, the total) is preferably 20 mol% or less with respect to all repeating units of the resin (A), and the pattern 15 mol% or less is more preferable from the viewpoint of more excellent internal void suppression and etching resistance. In addition, the lower limit of the content of the repeating unit (a2) is, for example, 3 mol% or more, and preferably 5 mol% or more with respect 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 desorbs by the action of an acid.

As a polar group, a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfo group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl) Imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, and tris Acidic groups such as (alkylsulfonyl) methylene groups (groups that dissociate in a 2.38% by mass tetramethylammonium hydroxide aqueous solution), and alcoholic hydroxyl groups.

In addition, the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded on an aromatic ring, and an aliphatic alcohol in which the α-position as a hydroxyl group is substituted with an electron withdrawing group such as a fluorine atom (e.g. For example, hexafluoroisopropanol group, etc.) are excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

As a preferable polar group, a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfo group are mentioned.

A group preferable as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group (leaving group) that leaves by the action of an acid.

As a group (leaving group) that is desorbed by the action of an acid, for example, -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), and the like.

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

Each of R ₀₁ and R ₀₂ independently represents 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, and for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, and oxy Tilgi, 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 thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic cycloalkyl group, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, a norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetra Cyclododecyl group, androstanyl group, etc. are mentioned. Further, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

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

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

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

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

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 group or a tertiary alkyl ester group is more preferable.

A repeating unit with a structure (acid-decomposable group) protected by a leaving group that decomposes and desorbs the -COO- group by the action of an acid

Resin (A) is a repeating unit having an acid-decomposable group, and it is preferable to have a repeating unit represented by the following general formula (AI).

[Formula 15]

In 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.

Each of Rx ₁ to Rx ₃ independently represents an alkyl group or a cycloalkyl group.

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

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

T is preferably a single bond or -COO-Rt-. Rt is preferably a C1-C5 chain alkylene group, more preferably -CH ₂ -, -(CH ₂ ) ₂ -, or -(CH ₂ ) ₃ -. It is more preferable that T is a single bond.

It is preferable that Xa ₁ is 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 has 1 to 4 carbon atoms, and includes a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group. It is preferable that the alkyl group of Xa _{1 is a methyl group.}

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and may be a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group. 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 group of Rx 1} , Rx ₂ and Rx ₃ , a part of the bond between carbons may be a double bond.

Examples _{of the cycloalkyl group of Rx 1} , Rx ₂ and Rx ₃ include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Cycloalkyl groups of the ring are preferred.

As _{a ring structure formed by bonding of two of Rx 1} , Rx ₂ and Rx ₃ , a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, or a norbornene ring, Polycyclic cycloalkyl rings, such as a tetracyclodecane ring, a tetracyclododecane ring, and an adamantane ring, are preferable. Among them, a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable. The structure shown below is also preferable as a ring structure formed by bonding of two of _{Rx 1} , Rx ₂ and Rx _3.

[Formula 16]

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

[Formula 17]

Resin (A), as a repeating unit having an acid-decomposable group, preferably has the repeating units described in paragraphs <0336> to <0369> of U.S. Patent Application Publication No. 2016/0070167A1.

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

A repeating unit with a structure (acid-decomposable group) protected by a leaving group that decomposes and desorbs phenolic hydroxyl groups by the action of an acid

Resin (A) is a repeating unit having an acid-decomposable group, and preferably has a repeating unit having a structure protected by a leaving group that decomposes and desorbs the phenolic hydroxyl group by the action of an acid. In addition, in this specification, a phenolic hydroxyl group is a group obtained by substituting a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and includes a benzene ring and a naphthalene ring.

As a leaving group that decomposes and desorbs by the action of an acid, for example, a group represented by the formulas (Y1) to (Y4) can be mentioned.

Equation (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ )

Equation (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 chain) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), _{at least two of Rx 1} to Rx ₃ are preferably methyl groups.

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

Two of Rx ₁ to Rx _{3 may be} bonded to form a monocyclic or polycyclic ring.

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

As _{the cycloalkyl group of Rx 1} to Rx ₃ , a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. desirable.

As _{a cycloalkyl group formed by bonding of two of Rx 1} to Rx ₃ , a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group Polycyclic cycloalkyl groups, such as such, are preferable. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.

In _{the cycloalkyl group formed by bonding of 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. .

The group represented by the formulas (Y1) and (Y2) _{is preferably an aspect in which Rx 1} is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to each other to form the cycloalkyl group described above.

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 bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. It is preferable that R ₃₆ is a hydrogen atom.

In formula (Y4), Ar represents an aromatic hydrocarbon group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to 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 that decomposes and desorbs a phenolic hydroxyl group by the action of an 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 the repeating unit having a structure (acid-decomposable group) protected by a leaving group that decomposes and desorbs a phenolic hydroxyl group 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 _{bonded to Ar 6} to form a ring, and R ₆₂ in that case 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 bonded to R 62} to form a ring, it represents a (n+2) valent aromatic hydrocarbon group.

In _{the case of n≥2, each of Y 2} independently represents a hydrogen atom or a group which is desorbed by the action of an acid. However, _{at least one of Y 2} represents a group that is desorbed by the action of an acid. It is preferable that the group which is desorbed by the action of an acid as Y _{2 is in the formulas (Y1) to (Y4).}

n represents the integer of 1-4.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (carbon number 1 to 4), halogen atom, hydroxyl group, alkoxy group (carbon number 1 to 4), carboxyl group, and alkoxycarbonyl group (carbon number 2 to 6). ) And the like, and those having 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 repeating units described above. Hereinafter, other repeating units that the resin (A) may contain will be described in detail.

(Repeating unit (a3) having a carboxy group)

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

Since the resin (A) contains the repeating unit (a3), the dissolution rate at the time of alkali development is more excellent.

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

[Formula 21]

Resin (A) may have the repeating unit (a3) individually by 1 type, and may have it using 2 or more types together.

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

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

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

When the resin (A) contains the repeating unit (a4), the dissolution rate at the time of alkali development is more excellent, and the etching resistance is excellent.

Although it does not specifically limit as a repeating unit which has a phenolic hydroxyl group, A hydroxystyrene repeating unit or a hydroxystyrene (meth)acrylate repeating unit is mentioned. As the repeating unit having a phenolic hydroxyl group, a repeating unit represented by the following general formula (I) is preferable.

[Formula 22]

In the formula,

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 _{bonded to Ar 4} to form a ring, and R ₄₂ in that case 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 connecting group.

Ar ₄ represents a (n+1) valent aromatic hydrocarbon group, _{and when bonded to R 42} to form a ring, it represents a (n+2) valent aromatic hydrocarbon group.

n represents the integer of 1-5.

In order to increase the polarity of the repeating unit represented by General Formula (I), it is also preferable that _{n is an integer of 2 or more, or that X 4} is -COO- or -CONR _{64 -.}

_{As the alkyl group represented by R 41} , R ₄₂ , and R ₄₃ in the general formula (I), a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group which may have a substituent , A C20 or less alkyl group such as a 2-ethylhexyl group, an octyl group, and a dodecyl group is preferable, a C8 or less alkyl group is more preferable, and a C3 or less alkyl group is more preferable.

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

_{Examples of the halogen atom represented by R 41} , R ₄₂ , and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group contained in the alkoxycarbonyl group represented by _{R 41} , R ₄₂ , and R ₄₃ in the general formula (I) is preferably the same as the alkyl _{group for R 41} , R ₄₂ , and R _43.

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

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

As a specific example of the (n+1) valent aromatic hydrocarbon group in the case where n is an integer of 2 or more, it is formed by removing (n-1) arbitrary hydrogen atoms from the above-described specific example of the divalent aromatic hydrocarbon group. The group is mentioned suitably.

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

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

-CONR ₆₄ represented by the X ₄ - alkyl group of R ₆₄ in (R ₆₄ is a hydrogen atom or an alkyl group), which may have a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n- view An alkyl group having 20 or less carbon atoms, such as a yl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, is preferable, and an alkyl group having 8 or less carbon atoms is 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 as the alkylene group, 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group which may have a substituent The alkylene group of 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, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, it is preferable that _{Ar 4 is a benzene ring group.}

Hereinafter, although a specific example of the repeating unit which has a phenolic hydroxyl group is shown, this invention is not limited to this. In the formula, a represents 1 or 2.

[Formula 23]

Resin (A) may have a repeating unit (a4) individually by 1 type, and may use 2 or more types together, and may have it.

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 with respect to all repeating units in the resin (A). desirable. In addition, the content of the repeating unit (a4) is preferably 85 mol% or less, and more preferably 80 mol% or less with respect to all repeating units in the resin (A).

(Repeat unit (a5))

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

As a lactone structure or a sultone structure, it is sufficient to have a lactone structure or a sultone structure, and a 5-7 membered cyclic lactone structure or a 5-7 membered sultone structure is preferable. Among them, in the form of forming a bicyclo structure or a spiro structure, a 5-7 membered ring lactone structure condensed with another ring structure, or a 5-7 membered ring sultone structure in the form of forming a bicyclo structure or a spiro structure. It is more preferable that other ring structures are condensed.

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

[Formula 24]

The lactone structure moiety or the sultone structure moiety may or may not have a _{substituent (Rb 2 ).} Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, and An ano group and an acid-decomposable group, etc., and a C1-C4 alkyl group, a cyano group, or an acid-decomposable group is preferable. n ₂ represents the integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

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

[Formula 25]

In the 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 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 is present, each of R 0} independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

Z represents a single bond, an ether bond, an ester bond, an amide bond, a uretein bond, or a urea bond. When a plurality of Z is present, each of Z independently represents a single bond, an ether bond, an ester bond, an amide bond, a uretein bond, or a urea bond.

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

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

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

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

Resin (A) may have a repeating unit which has a carbonate structure. It is preferable that the carbonate structure is a cyclic carbonate ester structure.

It is preferable that the repeating unit which has a cyclic carbonate ester structure is 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 of 0 or more.

R _A ² represents a substituent. When n is 2 or more _{, each of R A} ² independently represents a substituent.

A represents a single bond or a divalent linking group.

Z represents an atomic group forming a monocyclic structure or a polycyclic structure together with a 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 repeats described in paragraphs <0370> to <0414> of U.S. Patent Application Publication No. 2016/0070167A1 It is also preferred to have a unit.

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

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and specific examples of the monomer corresponding to the repeating unit represented by the general formula (A-1) will be given below, 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 can be optionally substituted with a lozen 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 having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure contained in the resin (A) (at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure) When a plurality of repeating units are present, the sum) is preferably 5 to 30 mol%, more preferably 10 to 30 mol%, and more preferably 20 to 30 mol% with respect to all repeating units in the resin (A). Is more preferred.

Resin (A), in addition to the above repeating structural units, further includes various repeating structural units for the purpose of controlling dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, or resolution, heat resistance, sensitivity, etc., which are general necessary properties of the resist. You may have it.

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

As a predetermined monomer, for example, one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. The compounds which have, etc. are mentioned.

In addition, an addition polymerizable unsaturated compound capable of copolymerizing with a monomer corresponding to the above various repeating structural units may be used.

In the resin (A), the molar content of 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 repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, and all of the repeating units are made of methacrylate repeating units and acrylate repeating units. Any of them can be used, but it is preferable that the acrylate-based repeating units are 50 mol% or less with respect to all repeating units of the resin (A).

(Repeating unit having an aromatic ring)

It is preferable that resin (A) has a repeating unit which has an aromatic ring. That is, it is preferable that at least any one of the repeating units 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 with respect to all repeating units in the resin (A), from the viewpoint of more excellent etching resistance. This is preferable, and 60 mol% or more is more preferable. In addition, 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.

(Polymerization method of resin (A))

Resin (A) can be synthesized according to an ordinary method (for example, radical polymerization). As a general synthesis method, for example, (1) a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and then polymerized by heating, and (2) a solution containing the monomer species and an initiator is added dropwise for 1 to 10 hours. A drop polymerization method added to the solvent may be mentioned, and among them, the drop polymerization method of (2) is preferable.

Examples of the reaction solvent 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, as well as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and cyclohexanone to be described later. And a solvent that dissolves the composition of the present invention. As the reaction solvent during polymerization, among others, it is preferable to use the same solvent as the solvent used in the composition of the present invention. This makes it possible to suppress the generation of particles during storage.

The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen and argon. In the polymerization reaction, it is preferable to use a commercially available radical initiator (for example, an azo initiator, and peroxide) as the 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 initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis(2-methylpropionate). .

In the polymerization reaction, as described above, a polymerization initiator may be optionally added. The method of adding the polymerization initiator into the system is not particularly limited, and may be added in a batch, or may be divided and added in a plurality of times. During the polymerization reaction, the solid content concentration of the reaction solution is usually 5 to 60 mass%, preferably 10 to 50 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 a method of collecting powder or solid content by adding it to a solvent.

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

Resin (A) may be used individually by 1 type, and may use 2 or more types together.

In the composition of the present invention, the content of the 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. Although the upper limit is not particularly limited, 99.5% by mass or less is preferable, 99% by mass or less is more preferable, and 98% by mass or less is still more preferable.

(Solid content concentration)

It is preferable that the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition of this invention is 10 mass% or more. As a result of this, for example, it becomes easy to form a pattern of a thick film having a film thickness of 1 μm or more (preferably 10 μm or more). Incidentally, the solid content concentration means a mass percentage of the mass of the resist components other than the solvent (components capable of constituting the resist film) with respect to the total mass of the composition of the present invention.

<Compound that generates acid by irradiation with actinic ray or radiation (mineral generator)>

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

The composition of the present invention is a compound that generates an acid by irradiation with actinic rays or radiation, and contains 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, 5-membered ring, or 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 reduction, and the reduction atom directly connected to ^{S + is a carbon atom.}

Each of R ^P1 to R ^P5 independently represents 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 (non-aromatic ring) or an aromatic ring, but it is preferably a non-aromatic ring.

The _{ring represented by Q 1} is a 4-membered ring, 5-membered ring, or 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 (non-aromatic ring) or an aromatic ring, but a non-aromatic ring is preferable. 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, and examples thereof include an alkyl group (preferably 1 to 6 carbon atoms), an electron withdrawing group (eg, acyl group, sulfonate group) and the like.

Ring Q ₁ has at least two carbon atoms as 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 reduction. The hetero atom referred to herein includes a hydrogen atom or a hetero atom to which a substituent is bonded in the case of a trivalent or higher hetero atom (for example, a nitrogen atom).

Examples of the hetero atom other than S ⁺ include an oxygen atom, a nitrogen atom, and a sulfur atom, and an oxygen atom or a 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 group as R P1} to R ^P5 may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. The alkyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom.

The number of carbon atoms of the aryl group as R ^P1 to R ^{P5 is preferably 6 to 10.} As said aryl group, a phenyl group etc. are mentioned, for example. The aryl group may have a substituent.

Although the ^{heteroaryl group as R P1} to R ^P5 is not particularly limited, it 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 group as R P1} to R ^P5 may be linear or branched. 1-10 are preferable and, as for the carbon number of the said alkoxy group, 1-6 are more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a tert-butoxy group. The alkoxy group may have a substituent, and the substituent is not particularly limited, but examples include an alkoxy group (e.g., an alkoxy group having 1 to 6 carbon atoms) or a cycloalkyl group (e.g., a cycloalkyl group having 5 to 10 carbon atoms). I 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 a hydroxyl group, an alkyl group, or an alkoxy group, and still more preferably an alkoxy group.

At least two of R ^P1 to R ^{P5 may} combine to form a ring. In the case of forming a ring, it is preferable that two adjacent two of ^{R P1} to R ^{P5 are bonded to form a ring.} The formed ring may be an aliphatic ring or an aromatic ring. Further, the formed ring may be a hydrocarbon ring or a hetero ring.

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

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

[Formula 30]

In General Formula (Z1), R ^Z1 represents an alkyl group.

[Chemical Formula 31]

In general formula (Z2),

Each of Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Multiple Xf's may be the same or different, respectively.

R ^Z2 and R ^Z3 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. ^{R Z2} and R ^Z3 in the case of a plurality of occurrences may be the same or different, respectively.

L ^Z1 represents a divalent linking group, and L ^Z1 may be the same as or different from each other in the case of a plurality of present.

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

x represents the integer of 1-20, and y represents the integer of 0-10. z represents the integer of 0-10.

[Formula 32]

In general formulas (Z3) and (Z4), Rb ₃ to Rb ₇ each independently represents an alkyl group, a cycloalkyl group, or an aryl group. Rb ₃ and Rb ₄ may be bonded to each other to form a ring structure. Rb ₅ and Rb ₆ may be bonded to each other 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 in the alkyl group is preferably 1 to 10, more preferably 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. The alkyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom, and a fluorine atom is preferable.

In General Formula (Z2), each of Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Multiple Xf's may be the same or different, respectively. 1-10 are preferable and, as for the carbon number of this alkyl group, 1-4 are more preferable. Moreover, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.

Xf is, it is more preferable that the fluorine atom or a perfluoroalkyl group having from 1 to 4 carbon atoms is preferred, and 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 group 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 a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. The alkyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom, and a fluorine atom is preferable. In the case where the alkyl group represents an alkyl group substituted with at least one fluorine atom, the preferred range is the same as that described for Xf.

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 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a combination of a plurality of these 2 A temporary connector, etc. are mentioned. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkyl A ene group- or -NHCO-alkylene group- is preferable, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene group- or -OCO-alkylene group- is more preferable.

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

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

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

The aryl group may be monocyclic or polycyclic. As this aryl group, a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group are mentioned, for example.

The heterocyclic group may be monocyclic or polycyclic. The polycyclic is more capable of suppressing the diffusion of acid. Moreover, the heterocyclic group may have aromaticity and does not need to have aromaticity. Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocycle not having aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the resin described above. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.

The cyclic organic group may have a substituent. As this substituent, for example, an alkyl group (either linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (any of monocyclic, polycyclic, and spiro rings may be used, and 3 to 20 carbon atoms are used). This is 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. have. In addition, carbon (carbon contributing to ring formation) constituting the cyclic organic group may be carbonyl carbon.

As an anion represented by the 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 ^- is -CF _{2 -CH (CF 3) -OCO- (} L Z1) q'-a Z1 is preferred. Here, L ^Z1 , z and A ^Z1 are the same as those in General Formula (Z2), respectively. q'represents the integer of 0-10.

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

Rb ₃ and Rb ₄ may be bonded to each other to form a ring structure. Rb ₅ and Rb ₆ may be bonded to each other to form a ring structure.

Although ^{the specific example of Z-} is shown below, it is not limited to these.

[Formula 33]

[Formula 34]

It is preferable that the compound represented by general formula (P-1) is a compound represented by the following general formula (P-2).

[Formula 35]

In the general formula (P-2),

Each of R ^P1 to R ^P5 independently represents 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 a ^{plurality of R P6} to R ^P9 exist respectively, they may be the same or different.

When m1 represents 2, two R ^P6 may be bonded to each other to form a ring.

When m2 represents 2, two R ^P8s may be bonded to each other to form a ring.

M ₁ represents a hetero atom 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.

The general formula (P-2) of, R ^P1 ~ ^P5 R, Z ^- is R ^P1 ~ ^P5 R, Z in each of the general formulas (P1) ^- is same as defined, it is also the same preferable range.

In the general formula (P-2), R ^P6 to R ^P9 each independently represent a hydrogen atom or a substituent. Although the substituent is not specifically limited, For example, an alkyl group (preferably C1-C6) is mentioned.

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

When a ^{plurality of R P6} to R ^P9 exist respectively, they may be the same or different.

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

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

In the general formula (P-2), M ₁ represents a hetero atom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent. It is preferable that M ₁ 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 more preferably an oxygen atom or a nitrogen atom. When a hetero atom can have a substituent, it may have a substituent. For example, when a hetero atom is a nitrogen atom, a group which lowers the basicity of a nitrogen atom is preferable as a substituent, and electron withdrawing groups, such as an acyl group and a sulfonate group, are mentioned. As an acyl group, a C1-C10 acyl group is preferable, and a C1-C5 acyl group is more preferable. As a sulfonate group, a C1-C10 sulfonate group is preferable, and a C1-C5 sulfonate group is more preferable.

It is preferable that the compound represented by general formula (P-1) is a compound represented by the following general formula (P-3).

[Chemical 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 a ^{plurality of R P6} to R ^P9 exist respectively, they may be the same or different.

When m1 represents 2, two R ^P6 may be bonded to each other to form a ring.

When m2 represents 2, two R ^P8s may be bonded to each other to form a ring.

M ₁ represents a hetero atom 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 be} bonded to form a ring.

Z ^- represents a non-nucleophilic anion.

The general formula (P-3) ^{of, R P1, R P2, R} P4, R P5, Z - is ^{R P1, R P2, R P4} , R P5, Z in each of the general formulas (P1) ^- and It has the same meaning, and the preferable range is also the same.

The general formula (P-3) ^{of, R P6 ~ R P9, m1} , m2, M 1 is the same meaning as ^{R P6 ~ R P9, m1,} m2, M 1 of each of the above-mentioned 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 a linear one is preferable. When R ^P12 represents an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, and a tert-butyl group. The alkyl group may have a substituent, and the substituent is not particularly limited, but examples include an alkoxy group (e.g., an alkoxy group having 1 to 6 carbon atoms) or a cycloalkyl group (e.g., a cycloalkyl group having 5 to 10 carbon atoms). I can.

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

It is particularly preferable that the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-4) or (P-5).

[Chemical 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.

A plurality of R ^P6 to R ^P9 may be the same or different, respectively.

Two R ^P6 may be bonded to each other to form a ring.

Two R ^P8 may be bonded to each other to form a ring.

M ₁ represents a hetero atom 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 be} bonded 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 , and Z ^{- are each of R P1} , R ^P2 , R ^{P4 in} the general formula (P-1), R ^P5, Z ^- is as defined, are also the same preferable range.

The general formula (P-4) and (P-5) of, ^P6 R R ~ ^P9 are the same meaning as R R ~ ^{P9 P6} in each of the general formula (P-2), are also the same preferable range.

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

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 lowers the basicity of the nitrogen atom is preferable, and electron withdrawing groups such as an acyl group and a sulfonate group are mentioned. As an acyl group, a C1-C10 acyl group is preferable, and a C1-C5 acyl group is more preferable. As a sulfonate group, a C1-C10 sulfonate group is preferable, and a C1-C5 sulfonate group is more preferable.

Specific examples of the compound represented by General Formula (P-1) are shown below, but are not limited thereto.

[Chemical Formula 39]

[Formula 40]

[Formula 41]

The compound represented by the general formula (P-1) can be synthesized by a known method (for example, the method described in Japanese Unexamined 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 compounds represented by the general formula (P-1) may be used alone or in combination of two or more.

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

[Photo-acid generators other than the compound represented by general formula (P-1)]

The composition of the present invention is a compound that generates an acid by irradiation with actinic rays 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.

As photoacid generators other than the compound represented by general formula (P-1), for example, a sulfonium salt compound, an iodonium salt compound, a diazonium salt compound, a phosphonium salt compound, an imide sulfonate compound, an oxime sulfonate compound, And a diazodisulfone compound, a disulfone compound, and an o-nitrobenzyl sulfonate compound.

As photoacid generators other than the compound represented by the general formula (P-1), a known compound that generates an acid by irradiation with actinic ray or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs [0125] to <0319> of U.S. Patent Application Publication No. 2016/0070167A1, paragraphs <0086> to <0094> of U.S. Patent Application Publication No. 2015/0004544A1, and U.S. Patent Application Publication No. 2016/0237190A1 The known compounds disclosed in paragraphs <0323> to <0402> can be suitably used.

As a photoacid generator other than the compound represented by general formula (P-1), a compound represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) is preferable, for example.

[Formula 42]

In the general formula (ZI),

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

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

Further, two of R ₂₀₁ to R _{203 may be} bonded to each other to form a ring structure, or an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group may be included in the ring. Examples of the group formed by bonding of two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group and pentylene group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

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

As a suitable embodiment of the cation in the general formula (ZI), a compound (Compound (ZI-3)) represented by a compound (ZI-1), a compound (ZI-2), a general formula (ZI-3) described later, and a general Corresponding groups in the compound (compound (ZI-4)) represented by formula (ZI-4) are mentioned.

Further, the photoacid generator other than the compound represented by the general formula (P-1) may be a compound having a plurality of structures represented by the general formula (ZI). For instance, with at least one of formulas (ZI) the compound of R ₂₀₁ ~ R ₂₀₃ shown by at least one of the another compound represented by formula (ZI) R ₂₀₁ ~ R _203, a single bond or a linking group It may be a compound having a structure bonded through it.

First, the 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 having arylsulfonium as a cation.

Aryl sulfonium compounds, the R ₂₀₁ to R ₂₀₃ all of the contributions is aryl, R ₂₀₁ to R ₂₀₃ are part of an aryl group, and the remaining credit is alkyl or cycloalkyl.

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

As the aryl group contained in the 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 having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, 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 a linear alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 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 (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 15 carbon atoms), and an aryl group (eg, carbon number 6 to 14), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be used as a substituent.

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

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

The _{organic group which does not have an aromatic ring as R 201} to R ₂₀₃ generally has 1 to 30 carbon atoms and preferably 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, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, or alkoxy It is a carbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

As _{the alkyl group and cycloalkyl group of R 201} to R ₂₀₃ , preferably, a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pen Tyl group), and a C3-C10 cycloalkyl group (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) are mentioned.

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

Next, the 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 is an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double At least one of the bonds may be included. 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. Each of R _x and R _y independently represents an alkyl group, a cycloalkyl group, or an alkenyl group. R _x and R _y may combine to form a ring. Further, at least two selected from M, R _6c and R _7c may be bonded to form a ring structure, or a carbon-carbon double bond may be included in the ring structure. Z ^- represents an anion.

In General Formula (ZI-3), as the alkyl group and cycloalkyl group represented by M, a linear alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), 3 to 15 carbon atoms (preferably 3 to 10 carbon atoms) A branched chain alkyl group or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms) is preferable, and specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group , A cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and a 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 having an oxygen atom or a sulfur atom or the like. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.

The said M may further have a substituent (for example, a substituent T). As this aspect, for example, a benzyl group etc. are mentioned as M.

Further, 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.

_Examples of the alkyl group, cycloalkyl group, and aryl group represented by R _6c and R 7c include those similar to those of M described above, and preferred embodiments thereof are also the same. Moreover, 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 those similar to those of M described above, and preferred embodiments thereof 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, a substituent T). As this aspect, 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 _x and R _y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), and specifically, 2-oxopropyl group, and 2-oxoview Tilgi, etc. are mentioned.

Examples of the alkoxycarbonylalkyl group represented by R _x and R _y include 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Moreover, R _x and R _y may be bonded to form a ring.

The _{ring structure formed by connecting R x} and R _y to each other 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 be bonded to each other to form a ring structure, and the formed ring structure may contain a carbon-carbon double bond.

Among them, the compound (ZI-3) is preferably a compound (ZI-3A).

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

[Formula 44]

In 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, a hydroxyl group , A nitro group, an alkylthio group or an arylthio group.

R _6c and R _{7c have the same meaning as those of R 6c} and R _7c in General Formula (ZI-3) described above, and their preferred embodiments are also the same.

R _x and R _{y have the same meaning as those of R x} and R _y in 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 x} and R _y may each be bonded to form a ring structure, and this ring structure is each independently an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon -It may contain a carbon double bond. Moreover, R _5c and R _6c , R _5c and R _x may each be bonded to form a ring structure, and the ring structures may each independently contain a carbon-carbon double bond. Moreover, R _6c and R _7c may be bonded to each other to form a ring structure.

Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by a combination of two or more of these rings. As a ring structure, a 3-10 membered ring is mentioned, A 4-8 membered ring is preferable, and a 5 or 6 membered ring is more preferable.

_Examples of the group formed by bonding of any two or more of R _1c to R _{5c, R 6c} and R _7c , and R _x and R _y , include a butylene group and a pentylene group.

The _{group formed by bonding of R 5c} and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

Zc ^- represents an anion.

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

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

[Formula 45]

In general formula (ZI-4),

l represents the integer of 0-2.

r represents the integer of 0-8.

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 more than one R ₁₄ is present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton. Show. These groups may have a substituent.

Each of R ₁₅ 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, a hetero atom such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. In one aspect, _{it is preferable that two R 15} are alkylene groups, and are bonded to each other to form a ring structure.

Z ^- represents an anion.

In General Formula (ZI-4), _{the alkyl group of R 13} , R ₁₄ and R ₁₅ is linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10. As the alkyl group, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are more preferable.

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

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

Examples of 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 chain alkyl group having 3 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), or A cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) is preferable.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R _{207 may each independently have a substituent.} Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include, for example, an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), and an aryl group ( For example, a C6-C15), an alkoxy group (for example, a C1-C15), a halogen atom, a hydroxyl group, a phenylthio group, etc. are mentioned.

Z ^- represents an anion.

In formula (ZI) Z ^-, Z in the general formula (ZII) ^-, and the general ^- Zc of the general formula (ZI-3A) ^-, the formula (ZI-3) Z in Z of formula according to (ZI-4) ^- as the preferable anion is represented by the following general formula (3).

[Formula 46]

In general formula (3),

o represents the integer of 1-3. p represents the integer of 0-10. q represents the integer of 0-10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. 1-10 are preferable and, as for the carbon number of this alkyl group, 1-4 are more preferable. Moreover, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.

Xf is, it is more preferable that the fluorine atom or a perfluoroalkyl group having from 1 to 4 carbon atoms is preferred, and a fluorine atom or CF _3. In particular, it is more preferable that both Xf are fluorine atoms.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a _{plurality of R 4} and R ₅ 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 a hydrogen atom.

The specific examples and suitable aspects of the alkyl group substituted with at least one fluorine atom are the same as those of the specific examples and suitable aspects of Xf in the general formula (3).

L represents a divalent connecting group. When a plurality of L exist, L may be the same or different, respectively.

As a divalent linking group, for example -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO- , -SO ₂ -, an alkylene group (preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a combination of a plurality of these 2 A temporary connector, etc. are mentioned. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkyl A ene group- or -NHCO-alkylene group- is preferable, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene group- or -OCO-alkylene group- is more preferable.

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

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

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

The aryl group may be monocyclic or polycyclic. As this aryl group, a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group are mentioned, for example.

The heterocyclic group may be monocyclic or polycyclic. The polycyclic is more capable of suppressing the diffusion of acid. Moreover, the heterocyclic group may have aromaticity and does not need to have aromaticity. Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocycle not having aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the resin described above. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.

The cyclic organic group may have a substituent. As this substituent, for example, an alkyl group (either linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (any of monocyclic, polycyclic, and spiro rings may be used, and 3 to 20 carbon atoms are used). This is 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. have. In addition, carbon (carbon contributing to ring formation) constituting the cyclic organic group 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 in General Formula (3). q'represents the integer of 0-10.

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

[Chemical Formula 47]

In general formula (4),

Each of X ^B1 and X ^B2 independently represents a hydrogen atom or a monovalent organic group having no fluorine atom. It is preferable that X ^B1 and X ^{B2 are hydrogen atoms.}

Each of X ^B3 and X ^B4 independently represents 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 more preferably both of X ^B3 and X ^B4 are a fluorine atom or a monovalent organic group having a fluorine atom. It is more preferable that both of X ^B3 and X ^B4 are an alkyl group substituted with a fluorine atom.

L, q, and W are the same as in General Formula (3).

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

In formula (ZI) Z ^-, Z in the general formula (ZII) ^-, and the general ^- Zc of the general formula (ZI-3A) ^-, the formula (ZI-3) Z in Z of formula according to (ZI-4) ^- as, it is also preferred the aromatic sulfonic acid anion represented by the general formula (SA1) shown below.

[Formula 48]

In formula (SA1),

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

n represents an integer of 0 or more. As n, 1-4 are preferable, 2-3 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 an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, an ester group, and a group consisting of a combination of two or more thereof.

B represents a hydrocarbon group.

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

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

[Formula 49]

General formula (ZI), the anion Z in the general formula (ZII) ^-, Z in the formula (ZI-3) ^-, in the general formula (ZI-3A) Zc ^-, and the general formula (ZI- ^{A preferable example of Z-} in 4) is the same as ^Z- in the compound represented by General Formula (P-1).

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

Photo-acid generators other than the compound represented by general formula (P-1) may be in the form of a low molecular weight compound, or may be a form introduced into a part of the polymer. Moreover, you may use together the form of a low molecular compound and the form introduced into a part of a polymer.

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

When photoacid generators other than the compound represented by general formula (P-1) are 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 still more preferably 1,000 or less.

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

Photoacid generators other than the compound represented by general formula (P-1) may be used individually by 1 type, and may use 2 or more types together.

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) 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 particularly preferably 1 to 15% by mass, based on the total solid content of the composition. Do.

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

<Acid diffusion control agent>

It is preferable that the composition of this invention contains an acid diffusion control agent. The acid diffusion control agent acts as a target for trapping an acid generated from a photoacid generator or the like during exposure and suppressing the reaction of the acid-decomposable resin in the unexposed portion by the excess generated acid. For example, a basic compound (DA), a basic compound (DB) whose basicity decreases or disappears by irradiation with actinic rays or radiation, an onium salt (DC) that is a relatively weak acid relative to an acid generator, and has a nitrogen atom. , A low molecular weight compound (DD) having a group that is desorbed by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation portion can be used as the acid diffusion controlling agent. In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs <0627> to <0664> of U.S. Patent Application Publication No. 2016/0070167A1, paragraphs <0095> to <0187> of U.S. Patent Application Publication No. 2015/0004544A1, and paragraphs of U.S. Patent Application Publication No. 2016/0237190A1 Known compounds disclosed in <0403> to <0423> and paragraphs <0259> to <0328> of U.S. Patent Application Publication No. 2016/0274458A1 can be suitably used as an acid diffusion control agent.

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

[Formula 50]

In general formulas (A) and (E),

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each independently a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms), or an aryl group (carbon number 6-20). R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

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

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

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

It is more preferable that the alkyl group in general formulas (A) and (E) is unsubstituted.

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

The basic compound (DB) whose basicity is lowered or lost by irradiation with actinic rays or radiation (hereinafter, also referred to as "compound (DB)") has a proton acceptor functional group, and is also subjected to irradiation with actinic rays or radiation. It is a compound that is decomposed by the method and changes from proton acceptor property to acidity or decreases, disappears, or changes from proton acceptor property to acidity.

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

[Formula 51]

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

The compound (DB) is decomposed by irradiation with actinic rays or radiation to generate a compound whose proton acceptor property decreases or disappears, or changes from proton acceptor property to acidity. Here, the decrease or disappearance of proton acceptor property, or the change from proton acceptor property to acidity, is a change in proton acceptor property caused by the addition of a proton to the proton acceptor functional group, and specifically, proton acceptor property. It means that when a proton adduct is produced from a compound (DB) having a functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.

The proton acceptor property can be confirmed by performing a pH measurement.

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

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in the Chemical Handbook (II) (Revised 4th Edition, 1993, Japanese Chemical Society edition, Maruzen Corporation). The lower the value of the acid dissociation constant pKa, the higher the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution can be measured by measuring the acid dissociation constant at 25°C using an infinitely diluted aqueous solution. Alternatively, using the following software package 1, a value based on a database of Hammet's substituent constants and known literature values can be calculated by calculation. The values of pKa described in the present specification all 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, an onium salt (DC), which is a relatively weak acid relative to the photoacid generator, can be used as the acid diffusion control agent.

When a photoacid generator and an onium salt that generates an acid, which is a relatively weak acid with respect to the acid generated from the photoacid generator, are mixed and used, the acid generated from the photoacid generator by irradiation with actinic rays or radiation causes unreacted weak acid anions. When it collides with a possessed onium salt, a weak acid is released through salt exchange to generate an onium salt having a strong acid anion. In this process, since the strong acid is exchanged for a weak acid having a lower catalytic ability, the acid is deactivated in appearance, and acid diffusion can be controlled.

As the onium salt which becomes relatively weak acid with respect to the photoacid generator, a compound represented by the following general formulas (d1-1) to (d1-3) is 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 represents a hydrocarbon containing a fluorine atom. Represents a 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.

It is preferable that carbon number of the hydrocarbon group represented by Z ^{2c is 1-30.}

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

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

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

Onium salts (DC), which are relatively weak acids with respect to the photoacid generator, have a cation moiety and an anion moiety in the same molecule, and a cation moiety and an anion moiety are connected by covalent bonds (hereinafter, "Compound (DCA) )").

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

[Chemical 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 a single bond connecting the cation site and the anion site.

-X ^{- _{is, -COO -, -SO 3 -,}} -SO 2 -, and -N ^- it represents an anion portion selected from -R _4. R ₄ is a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O) ₂ -), and a sulfinyl group (-S(=O)-) at a linking site with an adjacent N atom. ) Represents a monovalent substituent having at least one of.

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

Examples of the substituents having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, and An arylaminocarbonyl group and the like. Preferably, they are an alkyl group, a cycloalkyl group, or an 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 of these. The group etc. which are formed by combining are 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 of these.

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

As a group to be desorbed 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 preferred. It is more preferable.

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

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

[Chemical Formula 54]

In general formula (d-1),

Rb is each independently a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group (preferably Represents a C1-C10) or an alkoxyalkyl group (preferably C1-C10). Rb may be bonded to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, a functional group such as an oxo group, an alkoxy group Or may be substituted with a halogen atom. The same is true for the alkoxyalkyl group represented by Rb.

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

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

As a specific structure of the group represented by general formula (d-1), although the structure disclosed in paragraph <0466> of US 2012/0135348A1 can be mentioned, it is not limited to this.

It is preferable that the compound (DD) has a structure represented by the following general formula (6).

[Chemical Formula 55]

In general formula (6),

l represents the integer of 0-2, m represents the integer of 1-3, and l+m=3 is satisfied.

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

Rb has the same meaning as Rb in the 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 Ra are each independently an alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb, which are the same as the above-described groups. It may be substituted with a group.

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

Specific examples of the particularly preferred compound (DD) in the present invention include compounds disclosed in paragraph <0475> of US 2012/0135348A1, but are not limited thereto.

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter, also referred to as "compound (DE)") is preferably a compound having a basic moiety including 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 of the atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. In addition, from the viewpoint of improving basicity, it is preferable that an electron withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly connected to the nitrogen atom.

As a preferred specific example of the compound (DE), the compound disclosed in paragraph <0203> of US Patent Application Publication No. 2015/0309408A1 can be mentioned, but is not limited thereto.

A preferable example of an acid diffusion control agent is shown below.

[Chemical Formula 56]

[Chemical Formula 57]

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

The content of the acid diffusion control agent in the composition of the present invention (when multiple types are present, the total amount) 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. In addition, it is preferable that the hydrophobic resin is a resin different from the resin (A).

When the composition of the present invention contains a hydrophobic resin, it is possible to control a 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 traceability in immersion exposure, and reduce immersion defects.

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

The hydrophobic resin is a repeat having at least one selected from the group consisting of _{"fluorine atom", "silicon atom", and "CH 3} partial structure contained in the side chain portion of the resin" from the viewpoint of localization to the film surface layer. It is preferably a resin having a unit. When the hydrophobic resin contains a fluorine atom and/or a silicon atom, the fluorine atom and/or a 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.

It is preferable that the hydrophobic resin has at least one group selected from the group of the following (x) to (z).

(x) acidity

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

(z) groups that are decomposed by the action of acids

As the acid group (x), a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkyl Carbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group , And a tris(alkylsulfonyl)methylene group. As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis(alkylcarbonyl)methylene group is preferable.

Examples of the group (y) that is decomposed by the action of an alkali developer to increase the solubility in an 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-) and the like, and a lactone group or a carboxylic acid ester group (-COO-) is preferable. Examples of the repeating unit containing these groups are repeating units in which these groups are directly bonded to the main chain of a resin, and examples thereof include repeating units made of acrylic acid esters and methacrylic acid esters. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, this repeating unit may be introduced into the terminal of the resin by using a polymerization initiator or a chain transfer agent having these groups at the time of polymerization. As the repeating unit having a lactone group, the same repeating unit as the repeating unit having a lactone structure previously described in the section of Resin (A) can be mentioned.

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

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

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

On the other hand, particularly in _{the case where the hydrophobic resin contains a CH 3} partial structure in the side chain portion, the hydrophobic resin is also preferably a form in which substantially no fluorine atom and silicon atom are included. In addition, it is preferable that the hydrophobic resin is substantially composed of only 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 residual monomer and/or oligomer component contained in the hydrophobic resin is preferably 0.01 to 5% by mass, 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, a known resin can be appropriately selected and used alone or as a mixture thereof. For example, known resins disclosed in paragraphs <0451> to <0704> of US Patent Application Publication No. 2015/0168830A1 and paragraphs <0340> to <0356> of US Patent Application Publication No. 2016/0274458A1 are suitable as hydrophobic resins. Can be used. In addition, the repeating units disclosed in paragraphs <0177> to <0258> of U.S. Patent Application Publication No. 2016/0237190A1 are also preferable as repeating units constituting the hydrophobic resin.

Preferred examples of the monomers corresponding to the repeating units constituting the hydrophobic resin are shown below.

[Chemical Formula 58]

[Chemical Formula 59]

Hydrophobic resin may be used individually by 1 type, and may use 2 or more types together. It is preferable to mix and use two or more types of hydrophobic resins having different surface energies from the viewpoint of compatibility of immersion liquid followability and development characteristics in 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>

It is preferable that the composition of this invention contains a solvent. In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of U.S. Patent Application Publication No. 2016/0070167A1, paragraphs <0210> to <0235> of U.S. Patent Application Publication No. 2015/0004544A1, and paragraphs of U.S. Patent Application Publication No. 2016/0237190A1 Known solvents disclosed in <0424> to [0426] and paragraphs [0357] to <0366> of U.S. Patent Application Publication No. 2016/0274458A1 can be suitably used. As a solvent that can be used when preparing the composition, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably 4 carbon atoms) To 10), a monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), an alkylene carbonate, an alkyl alkoxyacetate, and an organic solvent such as alkyl pyruvate.

As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent not having a hydroxyl group may be used. As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-described exemplary compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable. More preferred are cholmonomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate. Moreover, as a solvent which does not have a hydroxyl group, alkylene glycol monoalkyl ether acetate, an alkylalkoxy propionate, a monoketone compound which may have a ring, a cyclic lactone, or an alkyl acetate, etc. are preferable. Among these, propylene glycol Lycol monomethyl ether acetate (PGMEA), ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferable, and propylene glycol monomethyl Etheracetate, γ-butyrolactone, ethylethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone are more preferred. As a solvent not having 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 having no hydroxyl group is preferable from the viewpoint of coating uniformity. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a sole solvent of propylene glycol monomethyl ether acetate, or two or more mixed solvents containing propylene glycol monomethyl ether acetate You can open it.

<Surfactant>

It is preferable that the composition of this invention contains a surfactant. In the case of containing a surfactant, a fluorine-based and/or silicone-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.

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, a pattern with good sensitivity and resolution and less adhesion and development defects can be obtained. As the fluorine-based and/or silicone-based surfactant, the surfactant described in paragraph <0276> of US 2008/0248425 A can be mentioned. Further, other surfactants other than the fluorine-based and/or silicone-based surfactants described in paragraph <0280> of US 2008/0248425 A may also be used.

These surfactants may be used alone or in combination of two or more. When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. On the other hand, when the content of the surfactant is 10 ppm (parts per million) or more with respect to the total solid content of the composition, the surface unevenness of the hydrophobic resin increases. Thereby, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and water followability at the time of immersion exposure is improved.

<Resin (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. It is preferable that resin (J) contains a repeating unit which has a phenolic hydroxyl group. In this case, typically, a negative pattern is suitably formed. Resin (J) may contain the above-described acid-decomposable group.

Although it does not specifically limit as a repeating unit which has a phenolic hydroxyl group contained in resin (J), It is preferable that it is a repeating unit represented by the following general formula (II).

[Chemical Formula 60]

In general formula (II),

R ₂ represents a hydrogen atom, an optionally substituted alkyl group (preferably a methyl group), or a halogen atom (preferably a fluorine atom).

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

Ar' represents an aromatic ring group.

m represents an integer of 1 or more. Resin (J) may be used individually by 1 type, and may use 2 or more types together. The content of the resin (J) in the total solid content of the composition of the present invention is generally 30% by mass or more, 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 still more preferably 85% by mass or less. As the resin (J), a resin disclosed in paragraphs <0142> to <0347> of U.S. Patent Application Publication No. 2016/0282720A1 can be suitably used.

(Other additives)

The composition of the present invention may further contain an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, or a dissolution accelerator. As a plasticizer, for example, polyalkylene glycol (as carbon number in an oxyalkylene unit, 2-6 are preferable, 2-3 are more preferable, 2-10 are preferable and 2-6 as an average addition number) More preferable). Specifically as a plasticizer, the following are mentioned, for example.

[Chemical Formula 61]

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

<How to prepare>

It is preferable that solid content concentration of the composition of this invention is 10 mass% or more, and it is preferable that the upper limit is about 50 mass% normally. As the solid content concentration of the composition of the present invention, among them, 10 to 50% by mass is more preferable, 25 to 50% by mass is more preferable, and 30 to 50% by mass is still more preferable. The solid content concentration is a mass percentage of the mass of the resist components other than 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 the purpose of increasing the number of processing stages and improving ion implantation resistance, the film thickness is 3 μm or more. It is preferable, and 5 micrometers or more are more preferable, and 10 micrometers or more are still more preferable. The upper limit is not particularly limited, but is, for example, 100 μm or less. Further, as described later, a pattern can be formed from the composition of the present invention. The film thickness of the pattern to be formed is preferably 1 μm or more, and 3 μm or more is preferable, 5 μm or more is more preferable, and 10 μm or more is more preferable for the purpose of increasing the number of processing stages and improving ion implantation resistance. 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, and after filtering it with a filter, and then applying it on a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 µm or less, more preferably 0.05 µm or less, and even more preferably 0.03 µm or less. In addition, when the solid content concentration of the composition of the present invention is high (e.g., 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 preferred. This filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In the filter filtration, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-062667 (Japanese Patent Application Laid-Open No. 2002-062667), cyclic filtration may be performed, and a plurality of types of filters may be arranged in series or in parallel. You may connect and perform filtration. Moreover, you may filter the composition multiple times. Further, before and after filter filtration, the composition may be subjected to a 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 from the viewpoint of more excellent coatability. In addition, the viscosity can be measured with an E-type viscometer.

<use>

The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties are changed by reacting by irradiation with actinic ray or radiation. More specifically, the composition of the present invention comprises a semiconductor manufacturing process such as an integrated circuit (IC), a circuit board such as a liquid crystal or a thermal head, a mold structure for imprinting, other photofabrication processes, or a flat plate printing plate. Or, it 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 redistribution formation process, and MEMS (Micro Electro Mechanical Systems).

[Pattern formation method]

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

The pattern formation method of the present invention,

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

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

(iii) A process (development process) of developing the exposed resist film using a developer is provided.

The pattern formation method of the present invention is not particularly limited as long as the steps (i) to (iii) are included, and may further have the following steps. In the pattern formation method of the present invention, the exposure method in the (ii) exposure step may be liquid immersion exposure. It is preferable that the pattern formation method of this invention includes (ii) an exposure process, and (iv) a preheating (PB: PreBake) process. It is preferable that the pattern formation method of this invention includes (ii) after an exposure process, and (iii) before a development process, and (v) post-exposure heating (PEB: Post Exposure Bake) process. The pattern formation method of the present invention may include the (ii) exposure step a plurality of times. The pattern formation method of the present invention may include (iv) a preheating step a plurality of times. The pattern formation method of the present invention may include (v) a heating step after exposure a plurality of times.

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

The support is not particularly limited, and in addition to the manufacturing process of a semiconductor such as an IC or a manufacturing process of a circuit board such as a liquid crystal or a thermal head, a substrate generally used in other photofabrication lithography processes, etc. 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, further preferably 80 to 130°C, in any of (iv) preheating step and (v) post-exposure heating step, and 80 ~120°C is most preferred. The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds in any of (iv) preheating step and (v) post-exposure heating step. Heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed using a hot plate or the like.

Although there is no limitation on the wavelength of the light source used in the exposure process, examples include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-ray, and electron beam. Among these, far ultraviolet light is preferable, and the wavelength is preferably 1 to 300 nm, more preferably 100 to 300 nm, and still more preferably 200 to 300 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., KrF excimer laser, ArF excimer laser, EUV or electron beam This is preferable, and a KrF excimer laser is more preferable.

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

As the alkali developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used. In addition, an aqueous alkali solution such as inorganic alkali, primary to tertiary amine, alcohol amine, and cyclic amine can also be used. Further, the alkali developer may contain an appropriate amount of alcohols and/or surfactants. The alkali concentration of the alkali developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15. The time to develop using an alkaline developer is usually 10 to 300 seconds. The alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.

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

As a ketone solvent, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amylketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetoneyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, Acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

As an ester solvent, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether acetate, Diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , Methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate. Can be lifted.

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

A plurality of the above-described solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, more preferably less than 10% by mass, and particularly preferably substantially no moisture. The content of the organic solvent to 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 with respect to the total amount of the developer. % Is particularly preferred.

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

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 with respect to the total amount of the developer.

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

As a developing method, for example, a method of immersing a substrate in a bath filled with a developer for a certain period of time (dip method), a method of stopping for a certain period of time by raising the developer on the surface of the substrate by surface tension (Puddle method), and A method of spraying a developer (spray method), or a method of continuously discharging a developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method), and the like.

The process of developing using an aqueous alkali solution (alkali developing process) and the process of developing using a developing solution containing an organic solvent (organic solvent developing process) may be combined. Thereby, pattern formation can be performed without dissolving only the region of intermediate exposure intensity, and thus a finer pattern can be formed.

(iii) After the developing step, it is preferable to include a step (rinsing step) of washing with a rinse liquid.

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

The rinse liquid used in the rinse process after the development process using the developer containing the 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 a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, and an ether-based solvent. desirable. Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent include those described for the developer containing an organic solvent. As the rinse liquid used in the rinse step in this case, a rinse liquid containing a monohydric alcohol is more preferred.

Examples of the monohydric alcohol used in the rinsing step 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. I can.

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

The rinse liquid may contain an appropriate amount of a surfactant. In the rinsing step, the developed substrate using an organic developer is cleaned using a rinsing liquid containing an organic solvent. The method of the cleaning treatment is not particularly limited, for example, a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (rotation coating method), a method of immersing the substrate in a bath filled with the rinse liquid for a certain period of time ( Dip method), or a method of spraying a rinse liquid onto the substrate surface (spray method). Among them, it is preferable to perform a cleaning treatment by a rotation coating method, and after cleaning, the substrate is rotated at a rotation speed of 2,000 to 4,000 rpm (revolution per minute) to remove the rinse liquid from the substrate. Moreover, it is also preferable to include a heating process (Post Bake) after a rinsing process. By this heating process, the developer and rinse liquid remaining between the patterns and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is usually 40 to 160°C, preferably 70 to 120°C, more preferably 70 to 95°C, and the heating time is usually 10 seconds to 3 minutes, and 30 seconds to 90°C. Candles are preferred.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention (e.g., resist solvent, developer, rinse liquid, composition for forming an antireflection film, or forming a top coat) It is preferable that the solvent composition etc.) do not contain impurities, such as a metal component, an isomer, and residual monomer. As the content of these impurities contained in the above various materials, 1 ppm or less is preferable, 100 ppt (parts per trillion) or less is more preferable, 10 ppt or less is more preferable, and does not contain substantially (detection limit of the measuring device The following) are particularly preferable.

As a method of removing impurities such as metals from the various materials, for example, filtration using a filter may be mentioned. As the filter pore diameter, the pore size is preferably 10 nm or less, more preferably 5 nm or less, and still 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 used which was previously washed with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel to be used. When using a plurality of types of filters, filters having different pore diameters and/or materials may be used in combination. Moreover, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulation filtration process. As the filter, it is preferable that the eluted material is reduced as disclosed in Japanese Patent Application Laid-Open No. 2016-201426 (Japanese Patent Application Laid-Open No. 2016-201426). In addition to filter filtration, impurities may be removed by an adsorbent, or filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent may be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon may be used. 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, as a method of reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting various materials, or a filter filtration is performed on the raw materials constituting various materials, or an apparatus A method such as distilling under conditions in which contamination is suppressed as much as possible by lining the inside with Teflon (registered trademark) may be mentioned. Preferred conditions for filter filtration performed on raw materials constituting various materials are the same as those described above.

In order to prevent the incorporation of impurities, the above various materials 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 of improving the surface roughness of the pattern may be applied to a 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 treating the pattern by plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957 may be mentioned. 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. 8328 83280N-1 A known method as described in "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. Hei 3-270227) and US Patent Application Publication No. 2013/0209941. Can be used as (Core).

[Method of manufacturing electronic device]

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

Example

Hereinafter, the present invention will be described in more detail based on examples. Materials, usage, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.

<resin>

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

[Formula 62]

[Chemical Formula 63]

[Formula 64]

[Formula 65]

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

(Measurement method of glass transition temperature of homopolymer)

The glass transition temperature of the homopolymer was measured by the differential scanning calorimetry (DSC) method when there was a catalog value or a literature value, and when there was a catalog value or a literature value, the value was taken. The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg was set to 18000, and the degree of dispersion (Mw/Mn) was set to 1.7. As the DSC device, a thermal analysis DSC differential scanning calorimeter Q1000 type manufactured by TA Instruments Japan Co., Ltd. was used, and the temperature increase rate was measured at 10°C/min. In addition, the homopolymer used for the measurement of Tg was synthesized by the following procedure using a corresponding monomer. In addition, the homopolymer is synthesized by a general dropping 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 liquid, 125 mass parts of a PGMEA solution containing 21 mass% of corresponding monomers and 0.35 mass% of dimethyl 2,2'-azobisisobutyrate were dripped over 6 hours. After completion of dropping, it stirred at 80 degreeC for 2 hours. The reaction solution was allowed to stand to cool, then reprecipitated and filtered with a large amount of methanol/water (mass ratio 9:1), 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 apparatus and the rate of temperature increase 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 the resins AX-1 and AX-2 was used as a homopolymer was 54°C.

[Formula 66]

[Chemical Formula 67]

<Acid Generator>

The structure of the photoacid generator used is shown below.

[Chemical Formula 68]

[Chemical Formula 69]

[Formula 70]

[Formula 71]

<Acid diffusion control agent>

The acid diffusion control agent used is shown below.

[Formula 72]

<Surfactant>

The surfactant used is shown below.

[Chemical Formula 73]

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

<Other additives>

Other additives used are shown below.

[Chemical Formula 74]

[Chemical Formula 75]

<solvent>

The solvent used is 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: 3-methoxypropionate methyl (MMP)

S-7: 3-methoxybutyl acetate

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

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

In Table 2, the content (mass%) of each component other than the solvent means the content ratio with respect to the total solid content. In addition, in Table 2, the content ratio (mass %) of the used solvent with respect to the total solvent was described.

[Table 2]

〔Pattern formation and various evaluations〕

<Pattern formation>

Using a spin coater ACT-8 made by Tokyo Electron, on a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazein, without providing an antireflection layer, while the resist composition prepared above was applied while the substrate was stationary. It was loaded. After dropping, the substrate is rotated, and the number of rotations is maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, additionally maintained at 500 rpm for 3 seconds, and again at 100 rpm for 2 seconds, and then the film thickness It was raised to the set rotational speed (1200 rpm) and maintained for 60 seconds. Thereafter, heat drying was performed on a hot plate at 130° C. for 60 seconds to form a positive resist film having a thickness of 11 μm. With respect to this resist film, a KrF excimer laser scanner (manufactured by ASML, PAS5500/) through a mask having a line-and-space pattern such that the space width of the pattern formed after reduction projection exposure and development is 5 μm and the pitch width is 25 μm. 850C wavelength 248nm) was used, and pattern exposure was carried out under exposure conditions of NA=0.60 and ?=0.75. After irradiation, bake at 120° C. for 60 seconds, immerse for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, rinse with pure water for 30 seconds, and dry, space width 5 μm, pitch width 25 μm Formed an isolated space pattern. The pattern exposure is exposure through a mask having a line and space pattern such that the space width after reduction projection exposure is 5 μm and the pitch width is 25 μm, and the exposure amount is an isolated space with a space width of 5 μm and a pitch width of 25 μm. It was set as the optimal exposure amount (sensitivity) (mJ/cm ² ) for forming a pattern. In the determination of the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM) (Hitachi High-Technologies Corporation 9380II). By the above procedure, a pattern was formed on the substrate.

<Performance evaluation>

Using a spin coater ACT-8 made by Tokyo Electron, on a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazein, without providing an antireflection layer, while the resist composition prepared above was applied while the substrate was stationary. It was loaded. After dropping, the substrate is rotated, and the number of rotations is maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, additionally maintained at 500 rpm for 3 seconds, and again at 100 rpm for 2 seconds, and then the film thickness It was raised to the set rotational speed (1200 rpm) and maintained for 60 seconds. Thereafter, heat drying was performed on a hot plate at 130° C. for 60 seconds to form a positive resist film having a thickness of 11 μm. A substrate (wafer) having a resist film was set in a dry etching apparatus (manufactured by Hitachi High Technologies, U-621), and with a CF ₄ , Ar, N ₂ mixed gas (gas ratio, 1:10:10), a gas pressure of 4 Pa, Plasma power 1600W, substrate bias 1200W, etching treatment for 30 seconds, O ₂ , CF ₄ mixed gas (gas ratio, 20:1), gas pressure 2Pa, plasma power 800W, substrate bias 0W for 60 seconds The etching treatment was continued, and the etching treatment was repeated six times each. The wafer after the etching treatment was broken, and the resist cross section was observed at a magnification of 10000 with a scanning electron microscope (SEM) (manufactured by Hitachi High Technologies, S-4800). Voids (voids) in the observed resist film were counted, and each of large voids (voids having a size of 50 nm or more) and small voids (voids having a size of less than 50 nm) was determined by 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 of Table 3, the resist composition of the example was able to suppress generation of large voids in the resist film, and also reduced small voids. Particularly in Examples, even the smallest voids having a size of less than 20 nm were not observed at all, or were less than 10 even if observed. Therefore, according to the resist composition of the embodiment, during etching, the actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern in which large voids and small voids are unlikely to occur in the pattern, the actinic ray-sensitive or sensitive A resist film formed from a radiation-sensitive resin composition, a pattern forming method using the actinic-ray-sensitive or radiation-sensitive resin composition, and a method of manufacturing an electronic device can be provided.

Claims (12)

As an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) and a compound that generates an acid by irradiation with actinic ray or radiation,
The resin (A) contains a repeating unit (a1) derived from a monomer having a glass transition temperature of 50° C. or less when used as a homopolymer, and a repeating unit (a2) having an acid-decomposable group,
The repeating unit (a1) is a non-acid-decomposable repeating unit,
The compound that generates an acid by irradiation with actinic ray or radiation includes a compound represented by the following general formula (P-1), an actinic ray-sensitive or radiation-sensitive resin composition.
[Formula 1]

In the general formula (P-1),
Q ₁ represents a ring containing S ^+.
Ring Q ₁ is a 4-membered ring, 5-membered ring, or 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 reduction, and the reduction atom directly connected to ^{S + is a carbon atom.}
Each of R ^P1 to R ^P5 independently represents 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 method according to claim 1,
The actinic ray-sensitive or radiation-sensitive resin composition wherein Q _{1 is a non-aromatic ring.} The method according to claim 1 or 2,
The actinic ray-sensitive or radiation-sensitive resin composition wherein Q ₁ ^{has a hetero atom other than S +} as reduction. The method according to claim 1 or 2,
The 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),
Each of R ^P1 to R ^P5 independently represents 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 a ^{plurality of R P6} to R ^P9 exist respectively, they may be the same or different.
When m1 represents 2, two R ^P6 may be bonded to each other to form a ring.
When m2 represents 2, two R ^P8s may be bonded to each other to form a ring.
M ₁ represents a hetero atom 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. The method according to claim 1 or 2,
The 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 a ^{plurality of R P6} to R ^P9 exist respectively, they may be the same or different.
When m1 represents 2, two R ^P6 may be bonded to each other to form a ring.
When m2 represents 2, two R ^P8s may be bonded to each other to form a ring.
M ₁ represents a hetero atom 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 be} bonded to form a ring.
Z ^- represents a non-nucleophilic anion. The method according to any one of claims 1 to 5,
The 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.
A plurality of R ^P6 to R ^P9 may be the same or different, respectively.
Two R ^P6 may be bonded to each other to form a ring.
Two R ^P8 may be bonded to each other to form a ring.
M ₁ represents a hetero atom 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 be} bonded 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. The method according to any one of claims 1 to 6,
An actinic ray-sensitive or radiation-sensitive resin composition having a solid content concentration of 10% by mass or more. The method according to any one of claims 1 to 7,
The actinic ray-sensitive or radiation-sensitive resin composition wherein Z ^- is an anion represented by any one 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),
Each of Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Multiple Xf's may be the same or different, respectively.
R ^Z2 and R ^Z3 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. ^{R Z2} and R ^Z3 in the case of a plurality of occurrences may be the same or different, respectively.
L ^Z1 represents a divalent linking group, and L ^Z1 may be the same as or different from each other in the case of a plurality of present.
A ^Z1 represents an organic group containing a cyclic structure.
x represents the integer of 1-20, and y represents the integer of 0-10. z represents the integer of 0-10.
[Formula 8]

In general formulas (Z3) and (Z4), Rb ₃ to Rb ₇ each independently represents an alkyl group, a cycloalkyl group, or an aryl group. Rb ₃ and Rb ₄ may be bonded to each other to form a ring structure. Rb ₅ and Rb ₆ may be bonded to each other to form a ring structure. The method according to any one of claims 1 to 8,
The actinic ray-sensitive or radiation-sensitive resin composition wherein the resin (A) has a repeating unit having an aromatic ring. A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9. (i) a step of forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 1 μm or more on a substrate by using an actinic ray-sensitive or radiation-sensitive resin composition,
(ii) the step of irradiating the actinic ray-sensitive or radiation-sensitive film with actinic ray or radiation having a wavelength of 200 to 300 nm, and
(iii) A pattern formation method having a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the 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 by irradiation with actinic ray or radiation,
The resin (A) contains a repeating unit (a1) derived from a monomer having a glass transition temperature of 50° C. or less when used as a homopolymer, and a repeating unit (a2) having an acid-decomposable group,
The repeating unit (a1) is a non-acid-decomposable repeating unit,
The compound that generates an acid by irradiation with actinic ray or radiation is an actinic ray-sensitive or radiation-sensitive resin composition comprising 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, 5-membered ring, or 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 reduction, and the reduction atom directly connected to ^{S + is a carbon atom.}
Each of R ^P1 to R ^P5 independently represents 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 for manufacturing an electronic device comprising the method for forming a pattern according to claim 11.