CN112602019A - Actinic-ray-or radiation-sensitive resin composition, resist film, pattern forming method, and method for manufacturing electronic device - Google Patents

Abstract

The present invention provides a photosensitive radiation-sensitive or radiation-sensitive resin composition, a resist film formed from the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition, and a photosensitive radiation-sensitive or radiation-sensitive resin composition using the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition A pattern forming method and a manufacturing method of an electronic device. The photosensitive radiation-sensitive or radiation-sensitive resin composition contains: a resin containing a non-acid-decomposable repeating unit derived from a monomer having a glass transition temperature of 50° C. or lower when used as a homopolymer, and having acid-decomposable repeatability a repeating unit of a group; and a compound represented by the general formula (P-1). Ring Q ₁ is a 4- to 6-membered ring. Among them, ring Q ₁ may form a condensed ring with other rings. As a ring element, ring Q ₁ has at least 2 carbon atoms, and the atom of the ring element directly bonded to S ⁺ is a carbon atom. R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. At least two of R ^P1 to R ^P5 may be bonded to form a ring. Z ^‑ represents a non-nucleophilic anion.

Description

Photosensitive radiation-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and manufacturing method of electronic device

technical field

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

Background technique

In order to compensate for the decrease in sensitivity due to light absorption after the resist is used for KrF excimer laser light (248 nm), an image forming method called chemical amplification is used as an image forming method for the resist. For example, an image forming method of positive chemical amplification includes an image forming method in which a photoacid generator in an exposed part is decomposed to generate an acid by exposing with excimer laser, electron beam, extreme ultraviolet light, or the like, and the exposure Post-baking (PEB: Post Exposure Bake) utilizes this generated acid as a reaction catalyst to convert an alkali-insoluble group into an alkali-soluble group, and removes the exposed portion with an alkali developer.

On the other hand, recently, the miniaturization of the wavelength of the exposure light source has gradually reached its limit. Especially in the injection process application and NAND memory (NOT AND memory), the three-dimensionalization of the memory layer for the purpose of increasing the capacity has gradually become mainstream. The three-dimensionalization of the memory layer requires an increase in the number of processing stages in the longitudinal direction, and therefore, the resist film is required to be thickened from the conventional nanometer size to the micrometer size.

For example, Patent Documents 1 and 2 describe chemically amplified positive photoresist compositions for thick films for forming a thick film photoresist layer.

Previous technical literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2007-206425

Patent Document 2: Japanese Patent Laid-Open No. 2008-191218

SUMMARY OF THE INVENTION

The technical problem to be solved by the invention

However, from the resist composition described in Patent Document 1 or 2, when etching the object to be etched using a pattern of a thick film formed by photolithography as a mask, pores (voids) were found to be dispersed inside the pattern. There are two types of pores having a size of 50 nm or more (also referred to as “macro pores”) and pores having a size of less than 50 nm (also referred to as “small pores”).

An object of the present invention is to provide a photosensitive radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern in which macrovoids and small pores are not easily generated in the pattern during etching, and a combination of the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin A resist film formed of a material, a pattern forming method using the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition, and a manufacturing method of an electronic device.

Means for solving technical problems

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the photosensitive radiation properties of a compound of a specific structure (photoacid generator of a specific structure) containing a specific resin and an acid that generates an acid upon irradiation with actinic rays or radiation (photoacid generator of a specific structure) Or a radiation-sensitive resin composition can solve the above-mentioned problems, and the present invention has been completed.

That is, the present inventors found that the above-mentioned object can be achieved by the following structure.

<1> A photosensitive radiation-sensitive or radiation-sensitive resin composition comprising a resin (A) and a compound that generates an acid upon irradiation with actinic rays or radiation, the photosensitive radiation-sensitive or radiation-sensitive resin composition middle

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

The above-mentioned repeating unit (a1) is a repeating unit that is not decomposable by acid,

The compound which generates an acid by irradiation with the above-mentioned actinic rays or radiation includes a compound represented by the following general formula (P-1).

[Chemical formula 1]

In the above general formula (P-1),

Q ₁ represents a ring containing S ⁺ .

Ring Q ₁ is a 4-membered ring, a 5-membered ring or a 6-membered ring. Among them, ring Q ₁ may form a condensed ring with other rings.

As a ring element, ring Q ₁ has at least 2 carbon atoms, and the atom of the ring element directly bonded to S ⁺ is a carbon atom.

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

Z ^- represents a non-nucleophilic anion.

<2> The photosensitive radiation-sensitive or radiation-sensitive resin composition according to <1>, wherein

The above-mentioned Q ₁ is a non-aromatic ring.

<3> The photosensitive radiation-sensitive or radiation-sensitive resin composition according to <1> or <2>, wherein

As a ring element, the above-mentioned Q ₁ has a hetero atom other than S ⁺ .

<4> The photosensitive radiation-sensitive or radiation-sensitive resin composition according to <1> or <2>,

in,

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

[Chemical formula 2]

In the above general formula (P-2),

R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. At least two of R ^P1 to R ^P5 may be bonded 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 are present, 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 heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.

Z ^- represents a non-nucleophilic anion.

<5> The photosensitive radiation-sensitive or radiation-sensitive resin composition according to <1> or <2>,

in,

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

[Chemical formula 3]

In the above 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 are present, 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 heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.

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

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

Z ^- represents a non-nucleophilic anion.

<6> The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of <1> to <5>, wherein

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

[Chemical formula 4]

[Chemical formula 5]

In the above 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.

The plurality of R ^P6 to R ^P9 may be the same or different.

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

Two R ^P8s may be bonded to each other to form a ring.

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

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

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

Z ^- represents a non-nucleophilic anion.

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

<7> The photosensitive radiation-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 photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of <1> to <7>, wherein

The above-mentioned Z ^- is an anion represented by any one of the following general formulae (Z1) to (Z4).

[Chemical formula 6]

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

[Chemical formula 7]

In general formula (Z2),

Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. A plurality of Xfs 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 them may be the same or different, respectively.

L ^Z1 represents a divalent linking group, and L ^Z1 may be the same or different when there are a plurality of them.

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

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

[Chemical formula 8]

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

<9> The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of <1> to <8>, wherein

The said resin (A) contains the repeating unit which has an aromatic ring.

<10> A resist film formed from the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of <1> to <9>.

<11> A pattern forming method comprising:

(i) a step of forming a photosensitive or radiation-sensitive film with a film thickness of 1 μm or more on a substrate by using a photosensitive or radiation-sensitive resin composition;

(ii) a step of irradiating actinic rays or radiation having a wavelength of 200 to 300 nm to the photosensitive radiation-sensitive or radiation-sensitive film; and

(iii) a step of developing the photosensitive radiation-sensitive or radiation-sensitive film irradiated with the above-mentioned actinic rays or radiation with a developer,

The above photosensitive radiation-sensitive or radiation-sensitive resin composition contains a resin (A) and a compound that generates an acid by irradiation with actinic radiation or radiation,

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

The above-mentioned repeating unit (a1) is a repeating unit that is not decomposable by acid,

The compound which generates an acid by irradiation with the above-mentioned actinic rays or radiation includes a compound represented by the following general formula (P-1).

[Chemical formula 9]

In the above general formula (P-1),

Q ₁ represents a ring containing S ⁺ .

Ring Q ₁ is a 4-membered ring, a 5-membered ring or a 6-membered ring. Among them, ring Q ₁ may form a condensed ring with other rings.

As a ring element, ring Q ₁ has at least 2 carbon atoms, and the atom of the ring element directly bonded to S ⁺ is a carbon atom.

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

Z ^- represents a non-nucleophilic anion.

<12> A manufacturing method of an electronic device including the pattern forming method according to <11>.

Invention effect

According to the present invention, it is possible to provide a photosensitive radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern in which macrovoids and small pores are not easily generated in the pattern during etching, and a combination of the photosensitive radiation-sensitive or radiation-sensitive resin can be provided. A resist film formed of a material, a pattern forming method using the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition, and a manufacturing method of an electronic device.

Detailed ways

Hereinafter, the present invention will be described in detail.

The description of the components described below may be completed based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment.

In this specification, "actinic ray" or "radiation" means, for example, the bright-line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electron beams (EB: Electron Beam) et al. "Light" in this specification means actinic rays or radiation. Unless otherwise specified, the term “exposure” in this specification includes not only exposure using the bright-line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also exposure using electron beams and A depiction of a particle beam such as an ion beam.

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

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

In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (also referred to as molecular weight distribution) (Mw/Mn) of a resin are defined by GPC (Gel Permeation Chromatography) )) device (HLC-8120GP C manufactured by TOSOH CORPORATION) for 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 detector (Refractive Index Detector)) polystyrene conversion value.

In the notation of groups (atomic groups) in the present specification, the notation not denoted as substituted or unsubstituted includes a group without a substituent and a group with a substituent. For example, "alkyl" means not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). Also, the "organic group" in the present specification refers to a group containing at least one carbon atom.

In addition, in this specification, when "it may have a substituent", the kind of the substituent, the position of the substituent, and the number of the substituent are not particularly limited. The number of substituents may be, for example, one, two, three or more. As an example of a substituent, a monovalent non-metallic atomic group other than a hydrogen atom can be mentioned, and can be selected from the following substituent T, for example.

(Substituent T)

Examples of the substituent T include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; phenoxy and p-tolyloxy, and the like. Aryloxy; alkoxycarbonyl such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acyloxy such as acetoxy, propionyloxy and benzoyloxy; acetyl, benzoyl, Acyl groups such as isobutyryl, acryloyl, methacryloyl and oxalyl; alkylsulfanyl such as methylsulfanyl and tert-butylsulfanyl; phenylsulfanyl and p-tolysulfanyl, etc. Arylsulfanyl; alkyl; cycloalkyl; aryl; heteroaryl; hydroxyl; carboxyl; formyl; sulfo; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonamido; silyl ; amino; monoalkylamino; dialkylamino; arylamino; and combinations thereof.

[Photosensitive radiation-sensitive or radiation-sensitive resin composition]

The photosensitive radiation-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 radiation or radiation, and the above-mentioned resin (A) Repeating unit (a1) derived from a monomer having a glass transition temperature of 50° C. or lower when used as a homopolymer, and repeating unit (a2) having an acid-decomposable group, the repeating unit (a1) It is a non-acid-decomposable repeating unit, and the compound which generates an acid by irradiation with the above-mentioned actinic rays or radiation includes a compound represented by the following general formula (P-1).

[Chemical formula 10]

In the above general formula (P-1),

Q ₁ represents a ring containing S ⁺ .

Ring Q ₁ is a 4-membered ring, a 5-membered ring or a 6-membered ring. Among them, ring Q ₁ may form a condensed ring with other rings.

As a ring element, ring Q ₁ has at least 2 carbon atoms, and the atom of the ring element directly bonded to S ⁺ is a carbon atom.

R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. At least two of R ^P1 to R ^P5 may be bonded 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-type resist composition or a negative-type resist composition. Moreover, the resist composition for alkali image development may be sufficient, and the resist composition for organic solvent image development may be sufficient. Among them, a positive resist composition and a resist composition for alkaline development are preferable.

The compositions of the present invention are typically chemically amplified resist compositions.

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 preferably does not contain a crosslinking agent.

The reason why the composition of the present invention can form a pattern in which macrovoids and small voids are less likely to be generated in the pattern during etching is not clear in detail, but is estimated as follows.

A resist film is formed using a resist composition containing an acid-decomposable resin and a photoacid generator, and the photoacid generator usually remains in a pattern (resist pattern) obtained by exposure and alkali development. In addition, in processes such as evacuation performed when the pattern is used as a mask to etch the object to be etched (typically plasma etching), it was found that macropores and macropores were generated due to the decomposition product of the photoacid generator remaining in the pattern. small pores.

The inventors of the present invention examined the following: as the acid-decomposable resin, a resin (resin (resin (resin (resin (resin (resin (resin (resin A)), thereby improving the plasticity of the pattern. Thereby, the decomposed product of the photoacid generator can be easily removed from the inside of the pattern by volatilization, and macrovoids can be reduced.

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

Therefore, the inventors of the present invention conducted intensive studies and found that if the cations of the photoacid generator decomposed by exposure are highly volatile, they are volatilized before etching, so that they do not remain in the pattern, and the generation of voids during etching can be suppressed. Furthermore, it was found that not only the macrovoids but also the small voids can be significantly reduced by using the resin (A) and the photoacid generator represented by the general formula (P-1) at the same time. In particular, it was found that very small pores with a size of less than 20 nm can also be reduced according to the present invention.

Furthermore, in the acid-decomposable resin (resin (A)) of the present invention, the repeating unit (a1) is a non-acid-decomposable repeating unit. This is because the repeating unit derived from a monomer having a glass transition temperature of 50° C. or lower when used as a homopolymer is an acid-decomposable repeating unit (for example, a repeating unit derived from t-butyl acrylate) that cannot be exhibited. the effect of the present invention. 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 unit proceeds. For example, a repeating unit derived from t-butyl acrylate undergoes a deprotection reaction to become a repeating unit derived from acrylic acid. Here, it is considered that acrylic acid is derived from a monomer having a glass transition temperature higher than 50° C. when used as a homopolymer, and therefore, 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 contains a repeating unit (a1) derived from a monomer having a glass transition temperature (Tg) of 50° C. or lower when used as a homopolymer, and has an acid-decomposable group The repeating unit (a2) of the above-mentioned repeating unit (a1) is a repeating unit that is not decomposable by acid.

Since resin (A) contains a repeating unit which has an acid-decomposable group, it is a resin (acid-decomposable resin) which decompose|disassembles by the action of an acid and increases in polarity. That is, in the pattern forming method of the present invention to be described later, typically, when an alkaline developer is used as the developer, a positive pattern can be preferably formed, and when an organic developer is used as the developer, a negative pattern can be preferably formed pattern.

(repeating 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 used as a homopolymer.

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

(Method for measuring glass transition temperature of homopolymer)

When there is a catalog value or a literature value, the glass transition temperature of the homopolymer adopts this value, and when it does not, it is measured by a differential scanning calorimetry (DSC: Differential scanning calorimetry) method. The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg was 18000, and the degree of dispersion (Mw/Mn) was 1.7. The thermal analysis DSC differential scanning calorimeter Q1000 type|mold by TA Instruments Japan Inc. was used as a DSC apparatus, and the measurement was performed at a temperature increase rate of 10 degreeC/min.

In addition, 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 mass parts of propylene glycol monomethyl ether acetate (PGMEA) were heated to 80 degreeC under nitrogen flow. While stirring this solution, 125 parts by mass of a PGMEA solution containing 21 mass % of the corresponding monomer and 0.35 mass % of dimethyl 2,2'-azobisisobutyrate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was further stirred at 80°C for 2 hours. After the reaction liquid was left to cool, reprecipitation and filtration were performed 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 used for DSC measurement. The DSC apparatus and the heating rate are as described above.

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

The repeating unit (a1) is preferably a non-acid-decomposable alkyl group having 2 or more carbon atoms, which can contain a hetero atom in the chain, from the viewpoint of easily volatilizing the low-molecular-weight compound remaining in the film to the outside of the system. repeating unit. In the present specification, "non-acid-decomposable" means having a property of not causing detachment/decomposition reaction by acid generated by the photoacid generator.

That is, more specifically, the "non-acid-decomposable alkyl group" includes an alkyl group that is not detached from the resin (A) by the action of an acid generated by a photoacid generator, or an alkyl group that is not decomposed by a photoacid generator. The alkyl group decomposed by the action of the generated acid.

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 that may contain a hetero atom in the chain will be described.

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

Examples of the alkyl group having 2 to 20 carbon atoms that may contain a hetero atom in the chain include one or more -CH ₂ - via -O-, -S-, -CO-, and -NR. ₆ - Or an alkyl group substituted with a divalent organic group obtained by combining two or more of these. The above-mentioned 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 that may contain a hetero atom in the chain include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, Octyl, nonyl, decyl, lauryl, octadecyl, isobutyl, sec-butyl, 1-ethylpentyl, 2-ethylhexyl, and one or more of these -CH ₂ -Monovalent alkyl substituted by -O- or -O-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).

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

[Chemical formula 11]

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

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 t-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.

It does not specifically limit as a cycloalkyl group represented by R< ₁ >, For example, a C5-C10 cycloalkyl group is mentioned, More specifically, a cyclohexyl group etc. are mentioned.

Among them, as R ₁ , a hydrogen atom or a methyl group is preferable.

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

In addition, the repeating unit (a1) may be a non-acid-decomposable alkyl group having a carboxyl group or a hydroxyl group that may contain a hetero atom in the chain, or A repeating unit of a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group which may contain a hetero atom in a ring element.

Next, the repeating unit having a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group that may contain a hetero atom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group that may contain a hetero atom in the ring element illustrate.

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

The carbon number 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 20 or less, for example, from the viewpoint that the Tg of the homopolymer is 50° C. or less.

The non-acid-decomposable alkyl group that 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 alkane having 2 to 20 carbon atoms that contains a hetero atom in the chain. base. In addition, at least one of the hydrogen atoms in the above-mentioned alkyl group is substituted with a carboxyl group or a hydroxyl group.

Examples of the alkyl group having 2 to 20 carbon atoms that may contain a hetero atom in the chain include one or more -CH ₂ - via -O-, -S-, -CO-, and -NR ₆ , for example. -Or an alkyl group substituted with a divalent organic group obtained by combining two or more of these. The above-mentioned R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

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

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

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

[Chemical 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 preferably 20, for example, from the viewpoint of setting the Tg of the homopolymer to 50° C. or lower. Below, it is more preferable that it is 16 or less, and it is still more preferable that it is 10 or less.

The non-acid-decomposable cycloalkyl group which may contain a hetero atom in the ring element is not particularly limited, and examples thereof include a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group) and a ring element A cycloalkyl group with 5 to 20 carbon atoms containing a heteroatom. In addition, at least one of the hydrogen atoms in the above-mentioned cycloalkyl group is substituted with a carboxyl group or a hydroxyl group.

Examples of the cycloalkyl group having 5 to 20 carbon atoms containing a hetero atom in the ring element include one or more -CH ₂ - by -O-, -S-, -CO-, and -NR, for example. ₆ - or a cycloalkyl group substituted with a divalent organic group obtained by combining two or more of these. The above-mentioned 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).

Among them, the non-acid-decomposable alkyl group having a carboxyl group or a hydroxyl group which may contain a hetero atom in the chain, or a ring element having a carboxyl group or a hydroxyl group which may contain a hetero atom, from the viewpoint of more excellent effects of the present invention Among the repeating units of a non-acid-decomposable cycloalkyl group, a repeating unit represented by the following general formula (1-3) is preferable.

[Chemical formula 13]

In the 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 carboxyl group or a hydroxyl group which may contain a hetero atom in the chain, or a non-acid-decomposable cycloalkyl group which may contain a hetero atom in a ring element and having a carboxyl group or a hydroxyl group.

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

_Definition and The preferred mode is as described above.

Among them, as R ₄ , a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group which may contain a hetero atom in a ring element is preferable.

Examples of monomer a1 include ethyl acrylate (-22°C), n-propyl acrylate (-37°C), isopropyl acrylate (-5°C), n-butyl acrylate (-55°C), methyl acrylate n-butyl acrylate (20°C), n-hexyl acrylate (-57°C), n-hexyl methacrylate (-5°C), n-octyl methacrylate (-20°C), 2-ethylhexyl acrylate (- 70℃), isononyl acrylate (-82℃), lauryl methacrylate (-65℃), 2-hydroxyethyl acrylate (-15℃), 2-hydroxypropyl methacrylate (26℃), 1-[2-(methacryloyloxy)ethyl succinate] (9°C), 2-ethylhexyl methacrylate (-10°C), sec-butyl acrylate (-26°C), methoxy Polyethylene glycol monomethacrylate (n=2) (-20°C), cetyl acrylate (35°C), etc. In addition, in parenthesis, Tg (degreeC) when it is a homopolymer is shown.

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

[Chemical formula 14]

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

In the resin (A), the content of the repeating unit (a1) (when there are a plurality of repeating units (a1), the total amount) is preferably 5 mol % or more, and more preferably 10 mol % or more with respect to all the repeating units of the resin (A). mol% or more, preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less. Among them, the content of the repeating unit (a1) in the resin (A) (the total when there are multiple repeating units (a1)) is preferably 5 to 50 mol % with respect to all the repeating units of the resin (A), more preferably It is 5-40 mol%, More preferably, it is 5-30 mol%.

(repeating unit (a2))

The resin (A) contains the 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 have 2 or more types together.

In the resin (A), the content of the repeating unit (a2) (the total when there are multiple repeating units (a2)) is preferably 20 mol % or less with respect to all the repeating units of the resin (A), from the inside of the suppression pattern From the viewpoint of excellent porosity and etching resistance, it is more preferably 15 mol% or less. In addition, the lower limit of the content of the repeating unit (a2) is, for example, 3 mol % or more, or preferably 5 mol % or more, based on all the repeating units of the resin (A).

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

Examples of the polar group include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfo group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, ( Alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkane) Acid groups (groups dissociated in 2.38 mass % tetramethylammonium hydroxide aqueous solution) ) and alcoholic hydroxyl groups, etc.

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 to an aromatic ring, and as a hydroxyl group, the α-position is substituted with an electron withdrawing group such as a fluorine atom. Aliphatic alcohols (for example, hexafluoroisopropanol, etc.) are excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less is preferable.

Preferable polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.

Groups preferable as acid-decomposable groups are groups in which hydrogen atoms of these groups are substituted with groups (leaving groups) that are detached by the action of an acid.

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

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

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

The alkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably alkyl groups having 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, and octyl. Base et al.

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. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include adamantyl, norbornyl, isobornyl, camphenyl, dicyclopentyl, α-pinenyl, Tricyclodecyl, tetracyclododecyl and androstane, etc. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom 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 anthracenyl 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 groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably alkenyl groups having 2 to 8 carbon atoms, and examples thereof include vinyl groups, allyl groups, butenyl groups, and cyclohexenyl groups.

The ring formed by R ₃₆ and R ₃₇ bonded 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 tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group.

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

A repeating unit having a structure (acid-decomposable group) in which the -COO- group is protected by a leaving group that is decomposed and released by the action of an acid

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

[Chemical 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.

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

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

As a divalent linking group of T, an alkylene group, an arylene group, -COO-Rt-, -O-Rt-, etc. are mentioned. In the formula, Rt represents an alkylene group, a cycloalkylene group or an arylene group.

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

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

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

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

The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, etc. As carbon number of an alkyl group, 1-10 are preferable, 1-5 are more preferable, and 1-3 are still more preferable. In the alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ , a part of the carbon-carbon bond may be a double bond.

As the cycloalkyl group for Rx ₁ , Rx ₂ and Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. are preferable Polycyclic cycloalkyl.

The ring structure formed by bonding two of Rx ₁ , Rx ₂ and Rx ₃ is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring and a cyclooctane ring, or a norbornyl ring Polycyclic cycloalkyl rings such as alkane ring, tetracyclodecane ring, tetracyclododecane ring and adamantane ring. 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 two of Rx ₁ , Rx ₂ and Rx ₃ .

[Chemical formula 16]

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (AI) are given below, but the present invention is not limited to these specific examples. The following specific example corresponds to the case where Xa ₁ in the 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.

[Chemical formula 17]

It is also preferable that the resin (A) has the repeating unit described in the paragraphs <0336> to <0369> of US Patent Application Publication No. 2016/0070167A1 as the repeating unit having an acid-decomposable group.

In addition, the resin (A) may have, as an acid, a repeating unit including a group decomposed by an acid to generate an alcoholic hydroxyl group described in paragraphs <0363> to <0364> of US Patent Application Publication No. 2016/0070167A1 A repeating unit of a decomposable group.

A repeating unit having a structure (acid-decomposable group) in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of an acid

As a repeating unit which has an acid-decomposable group, it is preferable that resin (A) contains the repeating unit which has the structure which has the structure which the phenolic hydroxyl group is decomposed|dissociated by the action of acid and is protected by the leaving group. In addition, in this specification, a phenolic hydroxyl group is a group which replaced the hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring, a naphthalene ring, and the like.

As a leaving group which decomposes and leaves|separates by the action of an acid, the group represented by formula (Y1) - (Y4) is mentioned, for example.

Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ )

Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ )

Formula (Y3): -C(R ₃₆ )(R ₃₇ )(OR ₃₈ )

Formula (Y4): -C(Rn)(H)(Ar)

In formulae (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). Among them, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), preferably at least two of Rx ₁ to Rx ₃ are methyl groups.

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

Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic ring or a 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, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

As the cycloalkyl group of Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are preferred. Cycloalkyl.

The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecyl group, or a tetracyclododecyl group. and polycyclic cycloalkyl groups such as adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.

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

Regarding the groups represented by the formulae (Y1) and (Y2), for example, an aspect in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group is preferable.

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. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. R ₃₆ is preferably a hydrogen atom.

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

The repeating unit having a structure (acid-decomposable group) in which the phenolic hydroxyl group is decomposed and released by the action of an acid is protected by a leaving group, preferably a hydrogen atom in the phenolic hydroxyl group represented by the formulae (Y1) to (Y4) A repeating unit of a group-protected structure.

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

[Chemical 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. Among them, R ₆₂ and Ar ₆ may be bonded to form a ring, and R ₆₂ in this 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 an (n+1)-valent aromatic hydrocarbon group, and when it is bonded to R ₆₂ to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group.

Regarding Y ₂ , when n≧2, each independently represents a hydrogen atom or a group detached by the action of an acid. Here, at least one of Y ₂ represents a group detached by the action of an acid. The groups to be removed by the action of an acid as Y ₂ are preferably the formulae (Y1) to (Y4).

n represents an integer of 1-4.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxy group. A carbonyl group (having 2 to 6 carbon atoms) or the like is preferably a substituent having 8 or less carbon atoms.

[Chemical formula 19]

[Chemical formula 20]

(other repeating units)

The resin (A) may contain other repeating units in addition to the repeating units described above. Hereinafter, other repeating units which the resin (A) may contain will be described in detail.

(repeating unit (a3) having a carboxyl group)

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

Resin (A) is more excellent in the dissolution rate at the time of alkali image development by containing the repeating unit (a3).

As a repeating unit (a3), the repeating unit derived from (meth)acrylic acid shown below is mentioned, for example.

[Chemical formula 21]

Resin (A) may have one type of repeating unit (a3) independently, and may have two or more types simultaneously.

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

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

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

Resin (A) is excellent in the dissolution rate at the time of alkali development by containing a repeating unit (a4), and is excellent in etching resistance.

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.

[Chemical 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. Among them, R ₄₂ and Ar ₄ may be bonded to form a ring, and R ₄₂ in this 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 linking group.

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

n represents an integer of 1-5.

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

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

The cycloalkyl group represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) may be monocyclic or polycyclic. Preferably, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as an optionally substituted cyclopropyl group, a cyclopentyl group, and a cyclohexyl group is used.

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, an iodine atom, and the like, and a fluorine atom is preferred.

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 in the above-mentioned R ₄₁ , R ₄₂ and R ₄₃ .

Preferable substituents among the above-mentioned groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a urea group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, and an alkoxy group. , a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, etc., preferably the number of carbon atoms in the substituent is 8 or less.

Ar ₄ represents an (n+1)-valent aromatic hydrocarbon group. When n is 1, the divalent aromatic hydrocarbon group may have a substituent. For example, arylene groups having 6 to 18 carbon atoms such as phenylene, tolylene, naphthylene, and anthracenyl, or thiophene and furan are preferable. , pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole and thiazole and other heterocyclic aromatic hydrocarbon groups.

As a specific example of the (n+1)-valent aromatic hydrocarbon group when n is an integer of 2 or more, from the above-mentioned specific example of the divalent aromatic hydrocarbon group, preferably any (n-1) pieces are removed. A group of hydrogen atoms.

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

Examples of substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n+1)-valent aromatic hydrocarbon group can have include R ₄₁ , R ₄₂ and R in the general formula (I), for example. Alkoxy groups such as those listed in ₄₃ ; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl; and the like.

The alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ is preferably methyl, ethyl, propyl, isopropyl, n-butyl which may have a substituent , sec-butyl, hexyl, 2-ethylhexyl, octyl, dodecyl and other alkyl groups having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms.

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

The divalent linking group of L ₄ is preferably an alkylene group, and the alkylene group is preferably an optionally substituted carbon atom such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. An alkylene group of numbers 1 to 8.

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

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

[Chemical formula 23]

Resin (A) may have one type of repeating unit (a4) independently, and may have two or more types simultaneously.

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 preferably 60 mol% or more with respect to all the repeating units in the resin (A). Moreover, 85 mol% or less is preferable with respect to all the repeating units in resin (A), and, as for content of repeating unit (a4), 80 mol% or less is more preferable.

(repeating unit (a5))

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

As a lactone structure or a sultone structure, what is necessary is just to have a lactone structure or a sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable. Among them, it is more preferable to form a lactone structure or a sultone structure in which other ring structures are condensed with a 5- to 7-membered cyclic lactone structure in the form of a bicyclic structure or a spiro ring structure, or other ring structures to form a bicyclic structure or a spiro ring structure In the form of a 5- to 7-membered ring sultone structure, a sultone structure or a sultone structure is condensed.

The resin (A) further preferably contains a lactone structure represented by any one of the following general formulae (LC1-1) to (LC1-21) or a lactone structure represented by the following general formulae (SL1-1) to (SL1-3) A repeating unit of a sultone structure represented by any of . In addition, the lactone structure or the sultone structure may be directly bonded to the main chain. As a preferable structure, the general formula (LC1-1), the general formula (LC1-4), the general formula (LC1-5), the general formula (LC1-8), the general formula (LC1-16) or the general formula can be mentioned. The lactone structure represented by the formula (LC1-21) or the sultone structure represented by the general formula (SL1-1).

[Chemical formula 24]

The lactone moiety or sultone moiety may or may not have a substituent (Rb ₂ ). Preferable substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and alkoxy groups having 1 to 8 carbon atoms. 8 is an alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, and the like, preferably an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) present may be the same or different. In addition, 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.

[Chemical formula 25]

In the above general formula (III),

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

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

R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are multiple R ₀ , each R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

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

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

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

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

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

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

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

[Chemical formula 26]

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

n represents an integer of 0 or more.

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

A represents a single bond or a divalent linking group.

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

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

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

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) are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to the case where R ₇ in the general formula (III) and R _A ¹ in the general formula (A-1) are methyl groups, but R ₇ and R _A ¹ can be optionally substituted with a hydrogen atom, halogen Atom or a monovalent organic group.

[Chemical formula 27]

In addition to the above-mentioned monomers, the monomers shown below can also be preferably used as the raw material of the resin (A).

[Chemical formula 28]

The content of the resin (A) having at least one repeating unit selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure (when there are a plurality of repeating units selected from the group consisting of a lactone structure, a sultone structure, and a sultone structure) At least one kind of repeating unit in the group of ester structure and carbonate structure is the total) with respect to all repeating units in the resin (A), preferably 5 to 30 mol %, more preferably 10 to 30 mol %, and further Preferably it is 20-30 mol%.

Resin (A) can adjust dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or properties generally required for resists, namely resolution, in addition to the repeating structural unit described above. Various repeating structural units are provided for the purpose of heat resistance, sensitivity, and the like.

Examples of such repeating structural units include repeating structural units corresponding to predetermined monomers, but are not limited to these.

As the predetermined monomer, for example, one selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like can be mentioned. Compounds of addition polymerizable unsaturated bonds, etc.

In addition to this, addition-polymerizable unsaturated compounds that can be copolymerized with monomers corresponding to the various repeating structural units described above can also be used.

In the resin (A), the content molar ratio of each repeating structural unit can be appropriately set in order to adjust various properties.

All of the repeating units of the resin (A) may be composed of (meth)acrylate-based repeating units. In this case, resins in which all repeating units are methyl acrylate-based repeating units, resins in which all repeating units are acrylate-based repeating units, and resins in which all repeating units are based on methyl acrylate-based repeating units and acrylate-based repeating units can be used. In either case, the acrylate-based repeating unit is preferably 50 mol % or less with respect to all the repeating units of the resin (A).

(repeating unit having an aromatic ring)

It is preferable that resin (A) contains the repeating unit which has an aromatic ring. That is, it is preferable that at least any one of repeating units in resin (A) is a repeating unit which has an aromatic ring.

From the viewpoint of being more excellent in etching resistance, the content of the repeating unit having an aromatic ring in the resin (A) is, for example, 40 mol % or more, preferably 55 mol % with respect to all repeating units in the resin (A). Above, more preferably 60 mol% or more. 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 conventional methods such as radical polymerization. As a general synthesis method, for example, (1) a general polymerization method in which a monomer species and an initiator are dissolved in a solvent and heated to perform polymerization, and (2) a monomer-containing monomer is added dropwise over 1 to 10 hours. A dropwise polymerization method in which a solution of a seed and an initiator is added to a heated solvent, etc., among them, the dropwise polymerization method of (2) is preferable.

Examples of the reaction solvent during polymerization include tetrahydrofuran, ethers such as 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, and propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and cyclohexanone, which will be described later, dissolve the composition of the present invention. solvent. Among them, the same solvent as the solvent used in the composition of the present invention is preferably used as the reaction solvent during the polymerization. Thereby, the generation of particulate matter during storage can be suppressed.

The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen and argon. It is preferable to use a commercially available radical initiator (for example, an azo-type initiator, a peroxide, etc.) as a polymerization initiator for a polymerization reaction. As the radical initiator, an azo-based initiator is preferable, and an azo-based initiator having an ester group, a cyano group, or a carboxyl group is more preferable. Examples of such azo-based initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), and the like .

As described above, the polymerization initiator can be optionally added during the polymerization reaction. The method of adding the polymerization initiator to the system is not particularly limited, and the system may be added in a lump or may be divided into multiple additions. During the polymerization reaction, the solid content concentration of the reaction liquid is usually 5 to 60% by mass, preferably 10 to 50% by mass. The reaction temperature is usually 10 to 150°C, preferably 30 to 120°C, and more preferably 60 to 100°C. After completion of the reaction, the polymer is recovered by a method such as a method of throwing into a solvent and recovering powder or solid content.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 30,000, still more preferably 3,000 to 25,000. 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, further 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 usually 20% by mass or more with respect to the total solid content in many cases, preferably 40% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass %above. The upper limit is not particularly limited, but is preferably 99.5% by mass or less, more preferably 99% by mass or less, and further preferably 98% by mass or less.

(solid content concentration)

The solid content concentration of the photosensitive radiation-sensitive or radiation-sensitive resin composition of the present invention is preferably 10% by mass or more. As a result, it becomes easy to form the pattern of the thick film whose film thickness is 1 micrometer or more (preferably 10 micrometers or more), for example. In addition, the solid content concentration refers to the mass percentage of the mass of other resist components (components capable of constituting a resist film) from which the solvent is removed with respect to the total mass of the composition of the present invention.

<A compound that generates an acid by irradiation with actinic rays or radiation (photoacid generator)>

[Compound Represented by General Formula (P-1)]

The composition of the present invention contains a compound represented by the following general formula (P-1) as a compound that generates an acid by irradiation with actinic rays or radiation.

[Chemical formula 29]

In the above general formula (P-1),

Q ₁ represents a ring containing S ⁺ .

Ring Q ₁ is a 4-membered ring, a 5-membered ring or a 6-membered ring. Among them, ring Q ₁ may form a condensed ring with other rings.

As a ring element, ring Q ₁ has at least 2 carbon atoms, and the atom of the ring element directly bonded to S ⁺ is a carbon atom.

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

Z ^- represents a non-nucleophilic anion.

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

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

The ring represented by Q ₁ may form a condensed ring with other rings. The other ring may be an alicyclic ring (non-aromatic ring) or an aromatic ring, but is preferably a non-aromatic ring. The other ring is preferably a 4-membered ring, a 5-membered ring or a 6-membered ring, 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 having 1 to 6 carbon atoms), an electron withdrawing group (eg, an acyl group, a sulfonate group), and the like.

As a ring element, ring Q ₁ has at least 2 carbon atoms, and the atom of the ring element directly bonded to S ⁺ is a carbon atom.

As a ring element, the ring Q ₁ preferably has a hetero atom other than S ⁺ . When the hetero atom referred to here is a hetero atom having a valence of three or more (for example, a nitrogen atom), it includes a hetero atom to which a hydrogen atom or a substituent is bonded.

As a hetero atom other than S ⁺ , an oxygen atom, a nitrogen atom, a sulfur atom, etc. are mentioned, Oxygen atom or a nitrogen atom is preferable.

In the above 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. 1-10 are preferable and, as for carbon number of the said alkyl group, 1-6 are more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, etc. are mentioned, for example. The said alkyl group may have a substituent, It does not specifically limit as a substituent, For example, a halogen atom is mentioned.

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 above-mentioned aryl group may have a substituent.

The heteroaryl group of R ^P1 to R ^P5 is not particularly limited, but an aromatic heterocyclic group containing at least one of a sulfur atom, a nitrogen atom, and an oxygen atom as a hetero atom in a ring element is preferable. The above-mentioned 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. As said alkoxy group, a methoxy group, an ethoxy group, a t-butoxy group, etc. are mentioned, for example. The alkoxy group may have a substituent, and the substituent is not particularly limited, and examples thereof include an alkoxy group (for example, an alkoxy group having 1 to 6 carbon atoms) or a cycloalkyl group (for example, an alkoxy group having 5 to 10 carbon atoms). cycloalkyl).

Preferably, at least one of R ^P1 to R ^P5 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 be bonded to form a ring. When forming a ring, two adjacent ones of R ^P1 to R ^P5 are preferably 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 heterocyclic ring.

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

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

[Chemical formula 30]

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

[Chemical formula 31]

In general formula (Z2),

Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. A plurality of Xfs 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 them may be the same or different, respectively.

L ^Z1 represents a divalent linking group, and L ^Z1 may be the same or different when there are a plurality of them.

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

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

[Chemical formula 32]

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

In general formula (Z1), R ^Z1 represents an alkyl group, and may be linear or branched. 1-10 are preferable and, as for carbon number of the said alkyl group, 1-6 are more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, etc. are mentioned, for example. Although the said alkyl group may have a substituent, it does not specifically limit as a substituent, For example, a halogen atom is mentioned, Preferably a fluorine atom is mentioned.

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

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ . In particular, Xf of both is more preferably a fluorine atom.

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

The alkyl groups represented by R ^Z2 and R ^Z3 may be linear or branched. 1-10 are preferable, as for the carbon number of the said alkyl group, 1-6 are more preferable, and 1-4 are still more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, etc. are mentioned, for example. Although the said alkyl group may have a substituent, it does not specifically limit as a substituent, For example, a halogen atom is mentioned, Preferably a fluorine atom is mentioned. When the alkyl group represents an alkyl group substituted with at least one fluorine atom, the preferable range is the same as the preferable range described in the above-mentioned Xf.

L ^Z1 represents a divalent linking group.

Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene (preferably having 1 to 6 carbon atoms), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms) ) and a bivalent linking group obtained by combining a plurality of them. Among them, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene- or -NHCO-alkylene-, more preferably -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene -.

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

As a cyclic organic group, an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example.

The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl, 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 anthracenyl group are mentioned, for example.

The heterocyclic group may be monocyclic or polycyclic. The polycyclic form can further inhibit the diffusion of the acid. In addition, the heterocyclic group may or may not have aromaticity. As an aromatic heterocyclic ring, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring are mentioned, for example. As a heterocyclic ring which does not have aromaticity, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring are mentioned, for example. As an example of a lactone ring and a sultone ring, the lactone structure and sultone structure illustrated in the said resin are mentioned. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferable.

The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, and spirocyclic). Any of the rings, preferably carbon number 3-20), aryl group (preferably carbon number is 6-14), hydroxyl, alkoxy, ester group, amide group, carbamate group, urea group , thioether group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon contributing to the formation of the ring) may be a carbonyl carbon.

As the 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 --CF ₂ ^-CH (CF ₃ )-OCO-(L ^Z1 )q'-A ^Z1 . Here, L ^Z1 , z and A ^Z1 are respectively the same as the anions in the general formula (Z2). q' represents an integer of 0-10.

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

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

Specific examples of Z ⁻ are shown below, but are not limited to them.

[Chemical formula 33]

[Chemical formula 34]

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

[Chemical formula 35]

In the above general formula (P-2),

R ^P1 to R ^P5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. At least two of R ^P1 to R ^P5 may be bonded 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 are present, 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 heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.

Z ^- represents a non-nucleophilic anion.

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

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

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

When a plurality of R ^P6 to R ^P9 are present, they may be the same or different.

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

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

In the above 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. Preferably M ₁ represents a heteroatom.

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 the hetero atom is a nitrogen atom, the substituent is preferably a group which reduces the basicity of the nitrogen atom, and examples thereof include electron withdrawing groups such as an acyl group and a sulfonate group. As the acyl group, an acyl group having 1 to 10 carbon atoms is preferable, and an acyl group having 1 to 5 carbon atoms is more preferable. As the sulfonate group, a sulfonate group having 1 to 10 carbon atoms is preferable, and a sulfonate group having 1 to 5 carbon atoms is more preferable.

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

[Chemical formula 36]

In the above 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 are present, 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 heteroatom or -CR ^P10 R ^P11 -. R ^P10 and R ^P11 each independently represent a hydrogen atom or a substituent.

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

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

Z ^- represents a non-nucleophilic anion.

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

In the above general formula (P-3), R ^P6 to R ^P9 , m1, m2 and M ₁ have the same meanings as R ^P6 to R ^P9 , m1, m2 and M ₁ in the above general formula (P-2), respectively, and preferably The range is also the same.

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

The alkyl group when R ^P12 represents an alkyl group may be linear or branched, but linear is preferred. When R ^P12 represents an alkyl group, the number of carbon atoms of the alkyl group is preferably 1-10, and more preferably 1-6. As said alkyl group, a methyl group, an ethyl group, a t-butyl group, etc. are mentioned, for example. The above-mentioned alkyl group may have a substituent, and the substituent is not particularly limited. For example, an alkoxy group (eg, an alkoxy group having 1 to 6 carbon atoms) or a cycloalkyl group (eg, a ring having 5 to 10 carbon atoms) may be mentioned. alkyl).

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 ones 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 heterocyclic ring.

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

[Chemical formula 37]

[Chemical formula 38]

In the above 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.

The plurality of R ^P6 to R ^P9 may be the same or different.

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

Two R ^P8s may be bonded to each other to form a ring.

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

R ^P12 represents a hydrogen atom or a substituent.

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

Z ^- represents a non-nucleophilic anion.

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

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

In the above general formulae (P-4) and (P-5), R ^P6 to R ^P9 have the same meanings as R ^P6 to R ^P9 in the above general formula (P-2), respectively, and the preferred ranges are also the same.

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

In the above 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 a nitrogen atom is preferable, and examples thereof include electron withdrawing groups such as an acyl group and a sulfonate group. As the acyl group, an acyl group having 1 to 10 carbon atoms is preferable, and an acyl group having 1 to 5 carbon atoms is more preferable. As the sulfonate group, a sulfonate group having 1 to 10 carbon atoms is preferable, and a sulfonate group having 1 to 5 carbon atoms is more preferable.

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

[Chemical formula 39]

[Chemical formula 40]

[Chemical formula 41]

The compound represented by the general formula (P-1) can be synthesized by a known method (for example, the method described in JP 2014-199389 A).

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

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

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

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

As a compound that generates an acid by irradiation with actinic rays or radiation, the composition of the present invention may further contain a compound represented by the general formula (P-1) in addition to the compound represented by the general formula (P-1). other photoacid generators.

Examples of photoacid generators other than the compound represented by the general formula (P-1) include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidesulfonate compounds, Oxime sulfonate compound, azo disulfone compound, disulfone compound and o-nitrobenzyl sulfonate compound.

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

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

[Chemical formula 42]

In the above general formula (ZI),

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

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

In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of groups that can be formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene, pentylene) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

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

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

In addition, 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 example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of the other compound represented by the general formula (ZI) may be a compound having a bond through a single bond or A compound with a structure bonded by a linking group.

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 of the general formula (ZI) is an aryl group, that is, a compound in which arylsulfonium is used as a cation.

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

As an arylsulfonium compound, a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an arylbicycloalkylsulfonium compound are mentioned, for example.

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

The alkyl group or cycloalkyl group which the arylsulfonium compound has as needed is a linear alkyl group having 1 to 15 carbon atoms, preferably a branched alkyl group having 3 to 15 carbon atoms, or a C3 to 15 carbon atomic alkyl group. Examples of the cycloalkyl group include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ may each independently have an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, C6-14), alkoxy group (for example, C1-15), halogen atom, hydroxyl group or phenylthio group are used as substituents.

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 without an aromatic ring. The aromatic ring here also contains an aromatic ring containing heteroatoms.

As an organic group which does not have an aromatic ring of R _<201 >-R _<203> , it is carbon number 1-30 normally, Preferably it is carbon number 1-20.

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

Preferred examples of the alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl and pentyl) and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl).

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

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

[Chemical formula 43]

In the 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 may include oxygen atoms, sulfur atoms, ester bonds, amide bonds and carbon-carbon double bonds. at least one of. 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 bond to form a ring. _Rx and _Ry each independently represent an alkyl group, a cycloalkyl group or an alkenyl group. R _x and R _y may be bonded to form a ring. In addition, at least two selected from M, R _6c and R _7c may be bonded to form a ring structure, and the ring structure may contain a carbon-carbon double bond. Z ^- represents an anion.

In the general formula (ZI-3), the alkyl group and cycloalkyl group represented by M are preferably linear alkyl groups having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), 3-15 (preferably carbon number 3-10) branched-chain alkyl group or carbon number 3-15 (preferably carbon number 1-10) cycloalkyl group, specifically, methyl group is mentioned , ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl and cyclohexyl and norbornyl.

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 containing a heterocyclic structure having an oxygen atom, a sulfur atom, or the like. As a heterocyclic structure, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, etc. are mentioned.

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

In addition, 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 the same groups as those of M described above, and the preferred embodiments thereof are also the same. In addition, R _6c and R _7c may bond to form a ring.

As a halogen atom represented by R _6c and R _7c , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

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

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

The above-mentioned R _x and R _y may further have a substituent (for example, a substituent T). As this aspect, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, etc. are mentioned as _Rx and _Ry , for example.

Examples of the 2-oxoalkyl group represented _by Rx and _Ry include groups having 1 to 15 carbon atoms (preferably, 1 to 10 carbon atoms), and specific examples include 2-oxoalkyl groups. propyl group and 2-oxobutyl group.

Examples of the alkoxycarbonylalkyl group represented _by Rx and _Ry include groups having 1 to 15 carbon atoms (preferably, 1 to 10 carbon atoms). In addition, R _x and R _y may be bonded to form a ring.

The ring structure in which R _x and R _y are bonded to each other may contain oxygen atoms, sulfur atoms, ester bonds, amide bonds or carbon-carbon double bonds.

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

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

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

[Chemical formula 44]

In the general formula (ZI-3A),

R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom , hydroxyl, nitro, alkylthio or arylthio.

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

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

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

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

A butylene group, a pentylene group, etc. are mentioned as a group formed by _combining any two or more of R _1c to R _5c , R _6c and R _7c , and Rx and R _y .

A single bond or an alkylene group is preferable as a group formed by bonding R _5c and R _6c and R _5c and R _x . As an alkylene group, a methylene group, an ethylene group, etc. are mentioned.

Zc ^- represents an anion.

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

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

[Chemical formula 45]

In general formula (ZI-4),

l represents an integer from 0 to 2.

r represents an integer of 0 to 8.

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

When more than one R ₁₄ exists, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a ring having a single ring or multiple rings An alkoxy group of an alkyl skeleton. These groups may have substituents.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have substituents. Two R _15s may be bonded to each other to form a ring.

When two R _15s 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 embodiment, two R _15s are preferably alkylene groups, which are mutually bonded to form a ring structure.

Z ^- represents an anion.

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

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

In general formulae (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 such as 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.

The alkyl and cycloalkyl groups of R ₂₀₄ to R ₂₀₇ are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, etc.). group, butyl group and pentyl group) or cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group and norbornyl group).

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

Z ^- represents an anion.

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

[Chemical formula 46]

In general formula (3),

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

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1-10, and more preferably 1-4. Also, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ . In particular, Xf of both is more preferably a fluorine atom.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₄ and R ₅ are present, R ₄ and R ₅ may be the same or different, respectively.

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

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

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

Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene (preferably having 1 to 6 carbon atoms), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms) ) and a bivalent linking group obtained by combining a plurality of them. Among them, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-, - CONH-alkylene- or -NHCO-alkylene-, more preferably -COO-, -OCO-, -CONH-, _-SO2- , -COO-alkylene- or -OCO-alkylene-.

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

As a cyclic organic group, an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example.

The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl, 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 anthracenyl group are mentioned, for example.

The heterocyclic group may be monocyclic or polycyclic. The polycyclic form can further inhibit the diffusion of the acid. In addition, the heterocyclic group may or may not have aromaticity. As an aromatic heterocyclic ring, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring are mentioned, for example. As a heterocyclic ring which does not have aromaticity, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring are mentioned, for example. As an example of a lactone ring and a sultone ring, the lactone structure and sultone structure illustrated in the said resin are mentioned. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferable.

The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either a straight chain or a branched chain, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be a monocyclic ring, a polycyclic ring, or a spiro group). Any of the rings, preferably carbon number 3-20), aryl group (preferably carbon number 6-14), hydroxyl, alkoxy, ester group, amide group, urethane group, urea group , thioether group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon contributing to the formation of the ring) may be a carbonyl carbon.

As the anion represented by the general formula (3), SO ₃ ^- -CF ₂ -CH ₂ -OCO-(L)q'-W, SO ₃ ^- -CF ₂ -CHF-CH ₂ -OCO-(L)q are preferable '-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 ( _CF3 )-OCO-(L)q'-W. Here, L, q and W are the same as the general formula (3). q' represents an integer of 0-10.

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

[Chemical formula 47]

In general formula (4),

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

X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. At least one of X ^B3 and X ^B4 is preferably a fluorine atom or a monovalent organic group having a fluorine atom, and both X ^B3 and X ^B4 are more preferably a fluorine atom or a monovalent organic group having a fluorine atom . Both of X ^B3 and X ^B4 are more preferably an alkyl group substituted with a fluorine atom.

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

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

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

[Chemical formula 48]

In formula (SA1),

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

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

D represents a single bond or a divalent linking group. As a divalent linking group, an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate group, an ester group, a combination of two or more of these groups, and the like are mentioned.

B represents a hydrocarbon group.

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

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

[Chemical formula 49]

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

The above-mentioned cations and anions can be used in any combination as a photoacid generator.

The photoacid generator other than the compound represented by general formula (P-1) may be the form of a low molecular compound, and the form of being incorporated in a part of polymers may be sufficient. Moreover, the form of a low molecular compound and the form of incorporating in a part of polymers can also be used simultaneously.

The photoacid generator other than the compound represented by the general formula (P-1) is preferably in the form of a low molecular compound.

When the photoacid generator other than the compound represented by general formula (P-1) is 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 photoacid generators other than the compound represented by general formula (P-1) are incorporated in a part of polymers, they may be incorporated in some of the aforementioned resins (A), or may be incorporated in In resins different from resin (A).

A photoacid generator 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) (there are various 0.1-35 mass % is preferable, 0.5-25 mass % is more preferable, 1-20 mass % is further more preferable, 1-15 mass % is especially preferable based on the total solid content of a composition.

When the compound represented by the above-mentioned general formula (ZI-3) or (ZI-4) is contained as the photoacid generator other than the compound represented by the general formula (P-1), the composition other than the compound represented by the general formula (ZI-3) or (ZI-4) is contained in the composition. The content of the photoacid generators other than the compound represented by formula (P-1) (the total amount in the case of multiple types) is preferably 1 to 35% by mass, more preferably 1 to 30% by mass based on the total solid content of the composition. quality%.

＜Acid Diffusion Control Agent＞

Preferably, the composition of the present invention contains an acid diffusion control agent. The acid diffusion control agent functions as a quencher that traps acid generated from a photoacid generator or the like during exposure, and suppresses the reaction of the acid-decomposable resin in the unexposed portion due to excess acid generation. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, an onium salt (DC) which becomes a relatively weak acid with respect to an acid generator, a nitrogen-containing A low molecular weight compound (DD) having an atom and a group detached by the action of an acid, an onium salt compound (DE) having a nitrogen atom in a cation moiety, or the like is used as an acid diffusion control agent. In the composition of the present invention, known acid diffusion control agents can be appropriately used. For example, paragraphs <0627> to <0664> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0095> to <0187> of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/0237190A1 Well-known compounds disclosed in paragraphs <0403> to <0423> of the specification and paragraphs <0259> to <0328> of US Patent Application Publication No. 2016/0274458A1 are preferably used as acid diffusion control agents.

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

[Chemical formula 50]

In general formulae (A) and (E),

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group. base (6 to 20 carbon atoms). 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 groups in the general formulae (A) and (E) may have a substituent or may be unsubstituted.

As the alkyl group having a substituent, the above-mentioned alkyl group 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.

More preferably, the alkyl groups in the general formulae (A) and (E) are unsubstituted.

The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine or piperidine, and more preferably has an imidazole structure or a diazabicyclic structure , compounds of onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives with hydroxyl and/or ether bonds or aniline derivatives with hydroxyl and/or ether bonds Wait.

The basic compound (DB) (hereinafter, also referred to as "compound (DB)") whose basicity is reduced or disappears by irradiation with actinic rays or radiation is a compound having a proton acceptor functional group and is irradiated by actinic rays or radiation. Compounds whose proton acceptor properties decrease or disappear or change from proton acceptor properties to acidity due to decomposition by irradiation.

The proton acceptor functional group refers to a group that can electrostatically interact with protons or a functional group having electrons, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having an unconjugated π-conjugation function. A functional group of nitrogen atoms that share an electron pair. The nitrogen atom having an unshared electron pair that does not contribute to π-conjugation refers to, for example, a nitrogen atom having a partial structure represented by the following formula.

[Chemical formula 51]

未共享电子对

E-pairs not shared

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

The compound (DB) produces a compound whose proton-accepting property decreases or disappears, or changes from proton-accepting property to acidity by being decomposed by irradiation with actinic rays or radiation. Here, the reduction or disappearance of the proton acceptor property or the change from the proton acceptor property to the acidity refers to the change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. When a proton adduct is formed between a compound (DB) of a physical functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.

The proton acceptor property can be confirmed by pH measurement.

The acid dissociation constant pKa of the compound (DB) that is decomposed by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably satisfies -13<pKa<-1, and further preferably satisfies -13<pKa< -3.

The acid dissociation constant pKa refers to the acid dissociation constant pKa in an aqueous solution, and is defined by, for example, Handbook of Chemistry (II) (Revision 4th Edition, 1993, edited by The Chemical Society of Japan, Maruzen. Inc.). The lower the value of the acid dissociation constant pKa, the greater the acid strength is shown. 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, the following software package 1 can be used to obtain a value based on a database of Hammett's substituent constant and known literature values by calculation. All pKa values described in the present specification represent values obtained by calculation using this software package.

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 for a photoacid generator, can be used as an acid diffusion control agent.

When a photoacid generator is used in combination with an onium salt that produces an acid that is relatively weaker than the acid generated by the photoacid generator, if the acid generated from the photoacid generator is irradiated with actinic rays or radiation, the acid generated by the photoacid generator and The onium salts of the unreacted weak acid anions collide, and the weak acid is released by salt exchange to produce an onium salt with a strong acid anion. In this process, the strong acid is exchanged for a weaker acid with lower catalytic performance, so the acid is deactivated in appearance and can control acid diffusion.

As an onium salt which becomes a relatively weak acid with respect to a photoacid generator, the compound represented by following general formula (d1-1) - (d1-3) is preferable.

[Chemical 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, Rf represents a hydrocarbon group containing a fluorine atom, and M ⁺ represents each independently Ammonium cation, sulfonium cation or iodonium cation.

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

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

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

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

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

The onium salt (DC) that becomes a relatively weak acid for the photoacid generator may be a compound having a cationic site and an anionic site in the same molecule, and the cationic site and the anionic site are linked by covalent bonds (hereinafter, also referred to as "compound (DCA)" )".).

As the compound (DCA), a compound represented by any one of the following general formulae (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 linking a cationic site and an anion site.

-X ^- represents an anion site selected from -COO ^- , -SO ₃ ^- , -SO ₂ ^- and -N ^- -R ₄ . R ₄ represents a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O) ₂ -), and a sulfinyl group (-S(=O)-) at the linking site with the adjacent N atom at least one of the monovalent substituents.

R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In addition, in the general formula (C-3), two of R ₁ to R ₃ together represent one divalent substituent, which may be bonded to an N atom via 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 alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, and an alkylamino group. Carbonyl, cycloalkylaminocarbonyl and arylaminocarbonyl, etc. Preferred is alkyl, cycloalkyl or aryl.

Examples of L ₁ of the divalent linking group include 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, a group formed by combining two or more of these, and the like. 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.

The low-molecular-weight compound (DD) (hereinafter, also referred to as "compound (DD)") which preferably has a nitrogen atom and has a group removed by the action of an acid has a group removed by the action of an acid on the nitrogen atom. group of amine derivatives.

The group to be released by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiacetal ether group, more preferably a carbamate group or Hemiacetal ether group.

100-1000 are preferable, as for the molecular weight of a compound (DD), 100-700 are more preferable, and 100-500 are still more preferable.

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

[Chemical formula 54]

In general formula (d-1),

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

The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R _b may be independently replaced by functional groups such as hydroxyl, cyano, amino, pyrrolidinyl, piperidinyl, morpholinyl, oxo, alkoxy, etc. or halogen atom substitution. The same applies to the alkoxyalkyl group represented by R _b .

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

Alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, derivatives thereof, and the like are exemplified as rings formed by linking two R _b to each other.

As a specific structure of the group represented by the general formula (d-1), the structure disclosed in the paragraph <0466> of the specification of US Patent Publication US2012/0135348A1 can be mentioned, but it is not limited thereto.

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

[Chemical formula 55]

In general formula (6),

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

R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two R _a may be the same or different, and the two R _a may be linked to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain hetero atoms other than the nitrogen atom in the formula.

R _b has the same meaning as R _b in the above-mentioned general formula (d-1), and the preferred examples are also the same.

In the general formula (6), the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group as R _a may each independently be substituted with the same groups as the aforementioned groups as the following groups: The alkyl group, cycloalkyl group, aryl group, aralkyl group as R _b may be substituted.

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

Specific examples of particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in the paragraph <0475> of US Patent Application Publication No. 2012/0135348A1.

The onium salt compound (DE) (hereinafter, also referred to as "compound (DE)") having a nitrogen atom in the cation part is preferably a compound having a basic site containing a nitrogen atom in the cation part. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. All atoms adjacent to the nitrogen atom in the basic site are further preferably hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving the basicity, it is preferable that the electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to the nitrogen atom.

Preferable specific examples of the compound (DE) include, but are not limited to, the compounds disclosed in the paragraph <0203> of US Patent Application Publication No. 2015/0309408A1.

Preferred examples of the acid diffusion control agent are shown below.

[Chemical formula 56]

[Chemical formula 57]

In the composition of the present invention, the acid diffusion control 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 (in the case of multiple types, the total amount) is preferably 0.05 to 10% by mass, and 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, the hydrophobic resin is preferably a resin different from the resin (A).

By containing the hydrophobic resin in the composition of the present invention, the static/dynamic contact angle on the surface of the photosensitive radiation or radiation sensitive film can be controlled. Thereby, developing characteristics can be improved, outgassing can be suppressed, immersion liquid followability during immersion exposure can be improved, and immersion defects can be reduced.

The hydrophobic resin is preferably designed to be biased on the surface of the resist film, but unlike surfactants, it is not necessary to have a hydrophilic group in the molecule, and it may not be effective for uniformly mixing polar/nonpolar substances .

From the viewpoint of being concentrated on the surface layer of the film, it is preferable that the hydrophobic resin contains at least one molecule selected from the group consisting of "fluorine atom", "silicon atom", and "CH ₃ moiety structure contained in the side chain moiety of the resin". A resin with repeating units. When the hydrophobic resin contains fluorine atoms and/or silicon atoms, the above-mentioned fluorine atoms and/or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chains.

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

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

(x) acid group

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

(z) Groups decomposed by the action of acids

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, and an (alkylsulfonyl)(alkylcarbonyl)idene group. Methyl, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene , bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene, etc. 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) decomposed by the action of an alkaline developing solution to increase the solubility with respect to the alkaline developing solution include a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C (O)OC(O)-), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (- OSO ₂ O-), sulfonate group (-SO ₂ O-), etc., preferably lactone group or carboxylate group (-COO-). The repeating unit containing these groups is, for example, a repeating unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include repeating units based on acrylates and methacrylates. In the repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit is used when polymerizing a polymerization initiator or chain transfer agent having these groups, and can be introduced into the terminal of the resin. As a repeating unit which has a lactone group, the same repeating unit as the repeating unit which has a lactone structure demonstrated previously in the term of resin (A) is mentioned, for example.

The content of the repeating unit having a group (y) which is decomposed by the action of an alkaline developing solution to increase the solubility with respect to the alkaline developing solution is preferably 1 to 100 mol % with respect to all repeating units in the hydrophobic resin, More preferably, it is 3-98 mol%, More preferably, it is 5-95 mol%.

The repeating unit having the group (z) decomposed by the action of an acid in the hydrophobic resin includes the same repeating unit as the repeating unit having an acid-decomposable group exemplified 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 the group (z) decomposed by the action of an acid is preferably 1 to 80 mol %, more preferably 10 to 80 mol %, and further preferably 20 mol % with respect to all repeating units in the hydrophobic resin. -60 mol%. The hydrophobic resin may further have repeating units different from the above-mentioned repeating units.

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

On the other hand, especially when the hydrophobic resin contains a CH ₃ moiety structure in a side chain part, an aspect in which the hydrophobic resin does not substantially contain a fluorine atom and a silicon atom is also preferable. Furthermore, it is preferable that the hydrophobic resin is substantially composed of repeating units composed of only 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 monomers and/or oligomer components contained in the hydrophobic resin is preferably 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass. In addition, the degree of dispersion (Mw/Mn) is preferably in the range of 1-5, and more preferably in the range of 1-3.

As the hydrophobic resin, known resins can be appropriately selected and used alone or as a mixture thereof. For example, as the hydrophobic resin, those described 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 can be appropriately used. Published known resins. In addition, the repeating units disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190A1 are also preferred 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]

One type of water-based resin may be used alone, or two or more types may be used in combination. It is preferable to mix and use two or more kinds of hydrophobic resins having different surface energies, from the viewpoint of both the liquid immersion liquid followability and the developing characteristics during liquid immersion exposure. The content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, and more preferably 0.05 to 8% by mass relative to the total solid content in the composition of the present invention.

＜Solvent＞

The composition of the present invention preferably contains a solvent. In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of the specification of US Patent Application Publication No. 2016/0070167A1, paragraphs <0210> to <0235> of the specification of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/ Well-known solvents disclosed in paragraphs [0424] to [0426] of the specification No. 0237190A1 and paragraphs [0357] to [0366] of the specification of US Patent Application Publication No. 2016/0274458A1. Examples of solvents that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, and alkyl alkoxypropionate. Esters, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and acetone Organic solvents such as acid alkyl esters.

As an organic solvent, the mixed solvent which mixed the solvent which has a hydroxyl group in a structure, and the solvent which does not have a hydroxyl group can be used. As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the aforementioned exemplified compounds can be preferably selected, and as the solvent including a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, and propylene glycol monomethyl ether is more preferable (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate. In addition, as the solvent not having a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound which may have a ring, cyclic lactone or alkyl acetate, etc. are preferable, Among them, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate is more preferable, and further preferable Propylene glycol monomethyl ether acetate, gamma-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone. 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. From the viewpoint of coating uniformity, a mixed solvent containing a solvent not having a hydroxyl group in an amount of 50% by mass or more is preferable. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate.

＜Surfactant＞

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

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, especially 220 nm or less is used, a pattern with favorable sensitivity and resolution can be obtained with few adhesion and development defects. As the fluorine-based and/or silicon-based surfactant, the surfactant described in the paragraph <0276> of US Patent Application Publication No. 2008/0248425 may be mentioned. In addition, other surfactants other than the fluorine-based and/or silicon-based surfactants described in the paragraph <0280> of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more. When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass relative to the total solid content of the composition. On the other hand, when the content of the surfactant is 10 ppm (parts per million: parts per million) or more with respect to the total solid content of the composition, the surface localization of the hydrophobic resin is improved. Thereby, the surface of the photosensitive radiation-sensitive film or the radiation-sensitive film can be made more hydrophobic, and the water followability at the time of liquid immersion exposure can be 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. The resin (J) preferably contains a repeating unit having a phenolic hydroxyl group. At this time, typically, a negative pattern is preferably formed. The resin (J) may contain the aforementioned acid-decomposable group.

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

[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. Content of resin (J) in the total solid of the composition of this invention is 30 mass % or more normally, Preferably it is 40 mass % or more, More preferably, it is 50 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 further preferably 85% by mass or less. As resin (J), resins disclosed in paragraphs <0142> to <0347> of US Patent Application Publication No. 2016/0282720A1 can be preferably used.

(other additives)

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

[Chemical formula 61]

These plasticizers may be used individually by 1 type, and may use 2 or more types together. When the composition of the present invention contains a plasticizer, the content of the plasticizer is preferably 0.01 to 20% by mass, and more preferably 1 to 15% by mass, based on the total solid content of the composition.

<Preparation method>

The solid content concentration of the composition of the present invention is preferably 10% by mass or more, and the upper limit is usually preferably about 50% by mass. Among them, the solid content concentration of the composition of the present invention is preferably 10 to 50% by mass, more preferably 25 to 50% by mass, and even more preferably 30 to 50% by mass. The solid content concentration refers to the mass percentage of the mass of the resist components other than the solvent with respect to the total mass of the composition.

In addition, the film thickness of the photosensitive radiation-sensitive or radiation-sensitive film (resist film) containing the composition of the present invention is preferably 1 μm or more, and is preferably 3 μm or more for the purpose of improving the injection resistance for increasing the number of processing steps, etc. It is more preferable that it is 5 micrometers or more, and it is still more preferable that it is 10 micrometers or more. The upper limit is not particularly limited, but is, for example, 100 μm or less. Moreover, as mentioned later, a pattern can be formed from the composition of this invention. The film thickness of the formed pattern is preferably 1 μm or more, and is preferably 3 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more for the purpose of improving the injection resistance for increasing the number of processing steps. The upper limit is not particularly limited, but is, for example, 100 μm or less.

The composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably in the above-mentioned mixed solvent, filtering it with a filter, and then applying it to 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 further preferably 0.03 μm or less. When the solid content concentration of the composition of the present invention is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and further It is preferably 0.3 μm or less. The filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. For filter filtration, as disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-062667 (Japanese Patent Laid-Open No. 2002-062667 ), filtration can be performed by performing circulatory filtration, or by connecting a plurality of filters in series or in parallel. Also, the composition may be filtered multiple times. In addition, the composition may be subjected to deaeration treatment or the like before and after the filter filtration.

The viscosity of the composition of the present invention is preferably 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 a photosensitive radiation-sensitive or radiation-sensitive resin composition whose properties are changed by reacting with actinic ray or radiation irradiation. More specifically, the composition of the present invention relates to a semiconductor production process such as an IC (Integrated Circuit), production of a circuit board such as a liquid crystal or a thermal head, production of a mold structure for imprinting, and others A photosensitive radiation-sensitive or radiation-sensitive resin composition used in a photo-etching process, a lithographic printing plate, or an acid-curable composition. In the present invention, the formed pattern can be used in an etching process, an ion implantation process, a bump electrode formation process, a rewiring formation process, MEMS (MicroElectro Mechanical Systems), and the like.

[Pattern formation method]

The present invention also relates to a pattern forming method using the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. In addition, together with the description of the pattern forming method, the photosensitive radiation-sensitive or radiation-sensitive film of the present invention is also described.

The pattern forming method of the present invention has the following steps:

(i) a step of forming a resist film (photosensitive radiation or radiation sensitive film) on a support by using the photosensitive radiation-sensitive or radiation-sensitive resin composition (resist film forming step);

(ii) a step of exposing (irradiating actinic rays or radiation) to the resist film (exposure step); and

(iii) The process (development process) of developing the said exposed resist film using a developing solution.

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

In the pattern formation method of this invention, the said (i) resist film formation process, (ii) exposure process, and (iii) development process can be performed by a generally known method. In the pattern forming method of the present invention, (i) in the resist film forming step, the film thickness of the photosensitive radiation-sensitive or radiation-sensitive film formed on the substrate is preferably 1 μm or more, and more preferably 3 μm or more, as described above. , more preferably 5 μm or more, particularly preferably 10 μm or more. The upper limit is not particularly limited, but is, for example, 100 μm or less. Furthermore, if necessary, a resist underlayer film (eg, 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 layer) may be formed on the upper layer of the resist film. As a protective film, a well-known material can be used suitably. For example, the specification of US Patent Application Publication No. 2007/0178407, the specification of US Patent Application Publication No. 2008/0085466, the specification of US Patent Application Publication No. 2007/0275326, the specification of US Patent Application Publication No. 2016/0299432, the specification of US Pat. The composition for forming a protective film disclosed in the specification of Patent Application Publication No. 2013/0244438 and the specification of International Patent Application Publication No. 2016/157988A. As the composition for forming a protective film, a composition containing the above-mentioned acid diffusion control agent is preferable. A protective film may be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.

The support is not particularly limited, and substrates commonly used in photolithography processes such as photolithography processes other than in the production process of semiconductors such as ICs and in the production process of circuit boards such as liquid crystals and thermal heads 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, still more preferably 80 to 130°C, and most preferably 80～120℃. The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds in any of the (iv) preheating step and the (v) post-exposure heating step. Heating can be performed by the mechanism with which an exposure apparatus and a developing apparatus are equipped, and a hotplate etc. can also be used for it.

The wavelength of the light source used in the exposure step is not limited, and examples thereof include infrared light, visible light, ultraviolet light, extreme ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among them, far-ultraviolet light is preferable, and the wavelength thereof is preferably 1 to 300 nm, more preferably 100 to 300 nm, and even 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 and ArF excimer laser are preferable Laser, EUV or electron beam, more preferably KrF excimer laser.

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

As an alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide is generally used, and other alkaline aqueous solutions such as inorganic bases, primary to tertiary amines, alcohol amines, and cyclic amines can also be used. In addition, the above-mentioned alkaline developer may contain an appropriate amount of alcohol and/or a surfactant. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15. The time for developing using an alkaline developer is usually 10 to 300 seconds. The alkali concentration, pH, and development time of the alkaline developer can be appropriately adjusted according to the pattern to be formed.

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

Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone), 4-heptanone, 1- Hexanone, 2-Hexanone, Diisobutylketone, Cyclohexanone, Methylcyclohexanone, Phenylacetone, Methylethylketone, Methylisobutylketone, Acetylacetone, Acetonylacetone, Violet Rothone, diacetone alcohol, acetyl methanol, acetophenone, methyl naphthyl ketone, isophorone and propylene carbonate, etc.

Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, and ethylene glycol. Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3- Butyl methyl-3-methoxyacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, 2-hydroxyisobutyl Methyl acetate, isoamyl acetate, isobutyl isobutyrate and butyl propionate, etc.

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

A plurality of the above-mentioned solvents may be mixed, or may be mixed with solvents other than the above or water. The moisture content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably not substantially containing water. The content of the organic solvent relative to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass relative to the total amount of the developer. quality%.

The organic developer may contain a known surfactant in an appropriate amount 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 relative to the total amount of the developer.

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

Examples of the developing method include: a method of immersing the substrate in a tank filled with a developer for a certain period of time (dipping method); ); the method of spraying the developer on the surface of the substrate (spray method); or the method of continuously spraying the developer while scanning the developer ejection nozzle at a certain speed on the substrate rotating at a certain speed (dynamic distribution method), etc.

You may combine the process of developing using an alkaline aqueous solution (alkaline developing process) and the process of developing using a developing solution containing an organic solvent (organic solvent developing process). Thereby, a pattern can be formed without dissolving only the region of the intermediate exposure intensity, so that a finer pattern can be formed.

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

As the rinsing liquid used in the rinsing step after the developing step using the 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 developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be additionally performed. Furthermore, after the rinsing process or the supercritical fluid-based process, a heat treatment may be performed in order to remove the moisture remaining in the pattern.

The rinsing liquid used in the rinsing step after the developing step using the organic solvent-containing developer 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, a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents is preferably used. Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent include the same solvents as those described in the organic solvent-containing developer. As a rinse liquid used in the rinse process at this time, the rinse liquid containing a monohydric alcohol is more preferable.

As the monohydric alcohol used in the rinsing step, linear, branched or cyclic monohydric alcohols can be mentioned. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl alcohol -2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-Octanol and methyl isobutyl methanol. 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 methyl alcohol. isobutyl methanol, etc.

A plurality of each component may be mixed, and organic solvents other than the above may be mixed and used. 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. By setting the water content to be 10% by mass or less, favorable developing characteristics can be obtained.

The rinse solution may contain a surfactant in an appropriate amount. In the rinsing step, the substrate developed with the organic-based developing solution is subjected to a cleaning process using a rinsing solution containing an organic solvent. The method of the cleaning treatment is not particularly limited, but for example, a method of continuously spraying a rinse liquid on a substrate rotating at a constant speed (spin coating method); immersing the substrate in a tank filled with the rinse liquid for a certain period of time method (dipping method); or a method of spraying rinsing liquid on the surface of the substrate (spray method), etc. Among them, it is preferable to perform a cleaning process by spin coating, and after cleaning, the substrate is rotated at a rotational speed of 2,000 to 4,000 rpm (revolution perminute) to remove the rinse liquid from the substrate. In addition, it is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinse solution remaining between the patterns and inside the patterns are removed by this heating step. 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, preferably 30 seconds to 30 seconds. 90 seconds.

The photosensitive radiation-sensitive or radiation-sensitive resin composition of the present invention and various materials used in the pattern forming method of the present invention (for example, a resist solvent, developer, rinse, composition for forming an antireflection film, or The composition for forming a top coat layer, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt (parts pertrillion: parts per million) or less, still more preferably 10 ppt or less, and particularly preferably not substantially contained (for detection by a measuring device) limit below).

As a method of removing impurities, such as a metal, from the above-mentioned various materials, the filtration using a filter is mentioned, for example. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. As the filter, a filter previously cleaned with an organic solvent may be used. In the filter filtration step, a plurality of types of filters can be connected in series or in parallel and used. When multiple filters are used, filters with different pore sizes and/or materials can also be used in combination. In addition, various materials may be filtered multiple times, and the process of performing multiple filtrations may be a circulation filtration process. As the filter, a filter with reduced eluates as disclosed in Japanese Patent Application Laid-Open No. 2016-201426 (Japanese Patent Application Laid-Open No. 2016-201426 ) is preferable. In addition to filter filtration, removal of impurities using an adsorbent may be performed, and filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. As the metal adsorbent, for example, the adsorbent disclosed in Japanese Patent Application Laid-Open No. 2016-206500 (Japanese Patent Application Laid-Open No. 2016-206500) can be mentioned. In addition, as a method for reducing impurities such as metals contained in the above-mentioned various materials, a method of selecting a raw material with a small metal content as a raw material constituting the various materials, filtering the raw materials constituting the various materials with a filter, or A method such as distillation is performed under conditions such as lining the apparatus with TEFLON (registered trademark) to suppress contamination as much as possible. Preferable conditions in the filter filtration of the raw materials constituting the various materials are the same as those described above.

In order to prevent contamination of impurities, the above-mentioned various materials are preferably stored in containers described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Laid-Open No. 2015-123351 ), and the like.

A method of improving the surface roughness of the pattern can also be applied to the pattern formed by the pattern forming method of the present invention. As a method of improving the surface roughness of a pattern, the method of processing a pattern with the plasma of the gas containing hydrogen which is disclosed in US Patent Application Publication No. 2015/0104957 can be mentioned, for example. In addition, Japanese Patent Application Laid-Open No. 2004-235468 (Japanese Patent Laid-Open No. 2004-235468), US Patent Application Laid-Open No. 2010/0020297, Proc.of SPIE Vol.8328 83280N-1 "EUV ResistCuring A known method described in "Technique for LWR Reduction and Etch Selectivity Enhancement". In addition, the pattern formed by the above method can be used, for example, as a spacer process ( Spacer Process) core material (Core).

[Manufacturing method of electronic device]

Furthermore, the present invention also relates to a method of manufacturing an electronic device including the above-described pattern forming method. The electronic device manufactured by the manufacturing method of the electronic device of the present invention can be suitably mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc. ).

Example

Hereinafter, the present invention will be described in further detail based on examples. The materials, usage amounts, ratios, processing contents, processing steps, 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 is not limitedly interpreted by the examples shown below.

＜Resin＞

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

[Chemical formula 62]

[Chemical formula 63]

[Chemical formula 64]

[Chemical formula 65]

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

(Method for measuring glass transition temperature of homopolymer)

When there is a catalog value or a literature value, the glass transition temperature of the homopolymer adopts this value, and when it does not, it is measured by a differential scanning calorimetry (DSC: Differential scanning calorimetry) method. The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg was 18000, and the degree of dispersion (Mw/Mn) was 1.7. The thermal analysis DSC differential scanning calorimeter Q1000 type|mold by TA Instruments Japan Inc. was used as a DSC apparatus, and the measurement was performed at a temperature increase rate of 10 degreeC/min. In addition, the homopolymer used for the measurement of Tg was synthesized by the following procedure using the corresponding monomer. In addition, the synthesis|combination of a homopolymer is performed by the usual dropping polymerization method. 54 mass parts of propylene glycol monomethyl ether acetate (PGMEA) were heated to 80 degreeC under nitrogen flow. While stirring this solution, 125 parts by mass of a PGMEA solution containing 21 mass % of the corresponding monomer and 0.35 mass % of dimethyl 2,2'-azobisisobutyrate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was further stirred at 80°C for 2 hours. After the reaction liquid was left to cool, reprecipitation and filtration were performed 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 used for DSC measurement. The DSC apparatus and the heating rate are as described above.

[Table 1]

In addition, the glass transition temperature when the monomer (ME-1) corresponding to the other repeating unit contained in resin AX-1 and AX-2 was made into a homopolymer was 54 degreeC.

[Chemical formula 66]

[Chemical formula 67]

<acid generator>

The structure of the photoacid generator used is shown below.

[Chemical formula 68]

[Chemical formula 69]

[Chemical formula 70]

[Chemical formula 71]

<Acid diffusion control agent> The acid diffusion control agent used is shown below.

[Chemical formula 72]

＜Surfactant＞

The surfactants used are shown below.

[Chemical formula 73]

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

＜Other additives＞

Other additives used are shown below.

[Chemical formula 74]

[Chemical formula 75]

＜Solvent＞

The solvents used are shown below.

S-1: Propylene Glycol Monomethyl Ether Acetate (PGMEA)

S-2: Propylene Glycol Monomethyl Ether (PGME)

S-3: Ethyl lactate (EL)

S-4: Ethyl 3-ethoxypropionate (EEP)

S-5: 2-heptanone (MAK)

S-6: methyl 3-methoxypropionate (MMP)

S-7: 3-methoxybutyl acetate

<Preparation of photosensitive radiation-sensitive or radiation-sensitive resin composition>

Each component shown in Table 2 was mixed so that it might become the solid content concentration (mass %) described in Table 2, and the solution was obtained. Next, the obtained solution was filtered with a polyethylene filter having a pore size of 3 μm, thereby preparing photosensitive radiation-sensitive or radiation-sensitive resin compositions (resist compositions) res-1 to res-21 , res-1X to res-4X. In addition, in a resist composition, solid content means all components except 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, Table 2 describes the content ratio (mass %) of the solvent used with respect to the total solvent.

[Table 2]

[Pattern formation and various evaluations]

<Pattern formation>

Using a spin coater ACT-8 manufactured by Tokyo Electron Limited, on a Si substrate (manufactured by Advanced Materials Technology Co., Ltd.) subjected to hexamethyldisilazane treatment, the antireflection layer was not provided, and the substrate was dropped while the substrate was stationary. The resist composition prepared above. After the dropwise addition, the substrate was rotated, and the rotation speed was maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, further at 500 rpm for 3 seconds, and at 100 rpm for 2 seconds, then increased to the film thickness setting rotation speed (1200 rpm) and maintained 60 seconds. Then, heat-drying was performed on a hot plate at 130° C. for 60 seconds to form a positive resist film with a film thickness of 11 μm. The resist film was subjected to pattern exposure, and a mask having a line and space pattern with a pattern space width of 5 μm and a pitch width of 25 μm formed by reduced projection exposure and development was scanned with a KrF excimer laser. instrument (manufactured by ASML, PAS5500/850C wavelength 248 nm), and performed under the exposure conditions of NA=0.60, σ=0.75. After irradiation, it was baked at 120° C. for 60 seconds, immersed in a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with pure water for 30 seconds, and dried to form a space with a width of 5 μm and a pitch of 5 μm. Isolated space pattern with a width of 25 μm. The above-mentioned pattern exposure is exposure through a mask having a line and space pattern to reduce the space width after projection exposure to 5 μm and the pitch width to 25 μm, and the exposure amount is set to form an isolated space with a space width of 5 μm and a pitch width of 25 μm. The most preferable exposure amount (sensitivity) (mJ/cm ² ) of the pattern. In the determination of the above-mentioned sensitivity, a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Corporation. 9380II) was used for the measurement of the spatial width of the pattern. Through the above steps, a pattern is formed on the substrate.

＜Performance evaluation＞

Using a spin coater ACT-8 manufactured by Tokyo Electron Limited, on a Si substrate (manufactured by Advanced Materials Technology Co., Ltd.) subjected to hexamethyldisilazane treatment, the antireflection layer was not provided, and the substrate was dropped while the substrate was stationary. The resist composition prepared above. After the dropwise addition, the substrate was rotated, and the rotation speed was maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, further at 500 rpm for 3 seconds, and at 100 rpm for 2 seconds, then increased to the film thickness setting rotation speed (1200 rpm) and maintained 60 seconds. Then, heat-drying was performed on a hot plate at 130° C. for 60 seconds to form a positive resist film with a film thickness of 11 μm. The substrate (wafer) having the resist film was set in a dry etching apparatus (manufactured by Hitachi High-Technologies Corporation, U-621), and the use of a mixed gas of CF ₄ , Ar and N ₂ (gas ratio was 1:10) was continued. : 10), etching treatment for 30 seconds under the conditions of gas pressure 4Pa, plasma power 1600W, substrate bias voltage 1200W, and using O ₂ , CF ₄ mixed gas (gas ratio is 20:1), with gas pressure 2Pa, The etching process for 60 seconds under the conditions of a plasma power of 800 W and a substrate bias of 0 W was repeated six times, respectively. The wafer after the etching process was disconnected, and the resist cross section was observed at a magnification of 10,000 using a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Corporation, S-4800). The observed pores (voids) in the resist film were counted, and macropores (pores with a size of 50 nm or more) and small pores (pores with a size of less than 50 nm) were determined according to the following criteria, respectively.

[Number of large pores]

A: 0 (not observed at all)

B: less than 10

C: 10 or more

[Number of small pores]

X: 0 (not observed at all)

Y: less than 10

Z: 10 or more

[table 3]

Number of macropores Number of small pores Example 1 A X Example 2 A Y Example 3 A Y Example 4 A X Example 5 A X Example 6 A X Example 7 A Y Example 8 A X Example 9 A Y Example 10 A Y Example 11 A X Example 12 A Y Example 13 A X Example 14 A X Example 15 A X Example 16 A X Example 17 A X Example 18 A X Example 19 A X Example 20 A X Example 21 A Y Comparative Example 1 A Z Comparative Example 2 C Z Comparative Example 3 B Y Comparative Example 4 B Z

As can be seen from the results in Table 3, the resist compositions of Examples suppressed the generation of macrovoids in the resist film, and also reduced small voids. In particular, in the Examples, very small pores with a size of less than 20 nm were not observed at all or less than 10 if they were observed. Therefore, according to the resist compositions of the examples, it is possible to provide a photosensitive radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern in which large pores and small pores are not easily generated in the pattern during etching, A resist film formed from a radiation-sensitive or radiation-sensitive resin composition, a method for forming a pattern using the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device.

Claims (12)

1. An actinic-ray-or radiation-sensitive resin composition comprising a resin (A) and a compound which generates an acid upon irradiation with actinic rays or radiation,

the resin (A) comprises a repeating unit a1 derived from a monomer having a glass transition temperature of 50 ℃ or lower when the resin is 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 which generates an acid by irradiation with actinic rays or radiation includes a compound represented by the following general formula (P-1),

in the above-mentioned general formula (P-1),

Q₁indicates that it contains S⁺The ring (a) of (b) is,

ring Q₁Is a 4-, 5-or 6-membered ring, wherein ring Q₁Can form a fused ring with other rings,

ring Q₁Has at least 2 carbon atoms as ring element, and S⁺The atoms of the directly bonded ring elements are carbon atoms,

R^P1～R^P5each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group, R^P1～R^P5At least 2 of which are optionally bonded to form a ring,

Z^-denotes a non-nucleophilic anion.

2. The actinic-ray-or radiation-sensitive resin composition according to claim 1, wherein,

said Q₁Is a non-aromatic ring.

3. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,

said Q₁In (b), as a ring element, has a structure other than S⁺A hetero atom other than the above.

4. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,

the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-2),

in the above general formula (P-2),

R^P1～R^P5each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group, R^P1～R^P5At least 2 of which are optionally bonded to form a ring,

R^P6～R^P9each independently represents a hydrogen atom or a substituent,

m1 and m2 each independently represent 1 or 2,

R^P6～R^P9when a plurality of them are present, they are optionally the same or different,

when m1 represents 2, 2R^P6Optionally bonded to each other to form a ring,

when m2 represents 2, 2R^P8Optionally bonded to each other to form a ring,

M₁represents a heteroatom or-CR^P10R^P11-，R^P10And R^P11Each independently represents a hydrogen atom or a substituent,

Z^-indicating non-nucleophilicityAn anion.

5. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,

the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-3),

in the above-mentioned general formula (P-3),

R^P1、R^P2、R^P4and R^P5Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group,

R^P6～R^P9each independently represents a hydrogen atom or a substituent,

m1 and m2 each independently represent 1 or 2,

R^P6～R^P9when a plurality of them are present, they are optionally the same or different,

when m1 represents 2, 2R^P6Optionally bonded to each other to form a ring,

when m2 represents 2, 2R^P8Optionally bonded to each other to form a ring,

M₁represents a heteroatom or-CR^P10R^P11-，R^P10And R^P11Each independently represents a hydrogen atom or a substituent,

R^P12represents a hydrogen atom or an alkyl group,

R^P1、R^P2、R^P4、R^P5and R^P12At least 2 of which are optionally bonded to form a ring,

Z^-denotes a non-nucleophilic anion.

6. The actinic-ray-or radiation-sensitive resin composition according to any one of claims 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),

in the above general formulae (P-4) and (P-5),

R^P1、R^P2、R^P4and R^P5Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group,

R^P6～R^P9each independently represents a hydrogen atom or a substituent,

there are a plurality of R^P6～R^P9Each of which is optionally the same or different,

2R^P6Optionally bonded to each other to form a ring,

2R^P8Optionally bonded to each other to form a ring,

M₁represents a heteroatom or-CR^P10R^P11-，R^P10And R^P11Each independently represents a hydrogen atom or a substituent,

R^P12represents a hydrogen atom or an alkyl group,

R^P1、R^P2、R^P4、R^P5and R^P12At least 2 of which are optionally bonded to form a ring,

Z^-represents a non-nucleophilic anion, and represents a non-nucleophilic anion,

in the above general formula (P-5), R^P13Represents a hydrogen atom or a substituent.

7. The actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein,

the solid content concentration is 10 mass% or more.

8. The actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein,

z is^-Is an anion represented by any one of the following general formulae (Z1) to (Z4),

in the general formula (Z1), R^Z1Represents an alkyl group, and is represented by,

in the general formula (Z2),

each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and Xf's present in plural are each optionally the same or different,

R^Z2and R^Z3Each independently represents a hydrogen atom, a fluorine atom or an alkyl group, and R when a plurality of R's exist^Z2And R^Z3Each of which is optionally the same or different,

L^Z1l represents a 2-valent linking group, and L when a plurality of groups are present^Z1Optionally the same or different, and optionally,

A^Z1represents an organic group containing a cyclic structure,

x represents an integer of 1 to 20, y represents an integer of 0 to 10, z represents an integer of 0 to 10,

in the general formulae (Z3) and (Z4), Rb₃～Rb₇Each independently represents an alkyl group, a cycloalkyl group or an aryl group, Rb₃And Rb₄Optionally bonded to form a ring structure, Rb₅And Rb₆Optionally bonded to form a ring structure.

9. The actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 8, wherein,

the resin (A) contains a repeating unit having an aromatic ring.

10. A resist film formed from the actinic-ray-or radiation-sensitive resin composition claimed in any one of claims 1 to 9.

11. A pattern forming method, comprising:

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

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

(iii) a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation with a developer,

the actinic-ray-or radiation-sensitive resin composition contains a resin (A) and a compound which generates an acid upon irradiation with actinic rays or radiation,

the resin (A) comprises a repeating unit (a1) derived from a monomer having a glass transition temperature of 50 ℃ or lower when the resin is 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 which generates an acid by irradiation with actinic rays or radiation includes a compound represented by the following general formula (P-1),

in the above-mentioned general formula (P-1),

Q₁indicates that it contains S⁺The ring (a) of (b) is,

ring Q₁Is a 4-, 5-or 6-membered ring, wherein ring Q₁Optionally forming a fused ring with other rings,

ring Q₁Has at least 2 carbon atoms as ring element, and S⁺The atoms of the directly bonded ring elements are carbon atoms,

R^P1～R^P5each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group, R^P1～R^P5At least 2 of which are optionally bonded to form a ring,

Z^-denotes a non-nucleophilic anion.

12. A method of manufacturing an electronic device, comprising the pattern forming method of claim 11.