JPWO2020049865A1 - Actinic light-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and manufacturing method of electronic device - Google Patents

Abstract

The resin (A) contains a resin (A), a compound (B) having a glass transition temperature of 100 ° C. or lower, and a solvent, and the resin (A) is a monomer having a glass transition temperature of 50 ° C. or lower when made into a homopolymer. The repeating unit (a1) to be derived and the repeating unit (a2) having an acid-degradable group are included, the repeating unit (a1) is a non-acid-degradable repeating unit, and the resin (A) is a non-acid-degradable repeating unit. It has a repeating unit having an aromatic ring, the content of the compound (B) is 1% by mass or more with respect to the total solid content, and the solid content concentration is 10% by mass or more. A radioactive resin composition, a resist film formed from the above composition, a pattern forming method using the above composition, and a method for producing an electronic device.

Description

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

Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method of the resist in order to compensate for the decrease in sensitivity due to light absorption. For example, as a method for forming an image of positive chemical amplification, exposure to an excimer laser, an electron beam, extreme ultraviolet light, or the like decomposes a photoacid generator in an exposed portion to generate an acid, and bake (PEB) after exposure. : A method of forming an image in which the generated acid is used as a reaction catalyst in Post Exposure Bake) to change an alkali-insoluble group into an alkali-soluble group, and an exposed portion is removed by an alkali developing solution.

On the other hand, in recent years, miniaturization using the wavelength of an exposure light source is reaching its limit, and especially in implanter process process applications and NAND memory (NOT AND memory), the memory layer has been made three-dimensional for the purpose of increasing the capacity. It is becoming mainstream. Since it is necessary to increase the number of processing steps in the vertical direction in order to make the memory layer three-dimensional, the resist film is required to be thickened from the conventional nano-sized film to the micron-sized film.

For example, Patent Document 1 describes a resist composition containing a resin having a glass transition temperature of 155 ° C. or higher, a compound having a glass transition temperature of 150 ° C. or lower, and a solvent.

International Publication No. 2017/110352

In order to form a memory with a three-dimensional structure, it is necessary to form various patterns using, for example, a thick resist film having a film thickness of 1 μm or more, and it is not only isolated spaces and contact holes, but also isolated. There is a need for a resist composition capable of forming a residual pattern, that is, an isolated line pattern, an isolated dot pattern, and the like.

The present inventors have studied the lithography characteristics of the resist composition described in Patent Document 1, and found that the resolution of the isolated pattern is not always sufficient and there is room for further improvement. I found. Specifically, it was found that in vacuuming after patterning or during etching after patterning, the isolated dot pattern may be peeled off from the substrate, resulting in poor resolution.

Further, when the resist composition described in Patent Document 1 was applied onto a substrate, the thick resist film obtained by drying was left to stand for a certain period of time, and then pattern exposure and development were performed, a desired line was obtained. It was found that CD (Critical Dimensions) fluctuations such as the width pattern not being obtained occur. That is, it was found that the resist composition described in Patent Document 1 has room for improvement in PCD (Post Coating Delay) performance.

Further, when etching is performed using a resist pattern formed from a thick resist film as a mask, it is required to suppress the occurrence of roughness on the side wall of the resist pattern and reduce the development residue.

According to the present invention, when a pattern is formed from a thick resist film (for example, having a thickness of 1 μm or more), the resolution of the unisolated pattern is excellent, and the development residue after the development of the pattern can be reduced. Provided are a sensitive light-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method for manufacturing an electronic device, which have excellent PCD performance and can suppress roughness on the side wall of a pattern that may occur during etching. The task is to do.

As a result of diligent studies to solve the above problems, the present inventors have found that according to a sensitive light-sensitive or radiation-sensitive resin composition containing a specific resin and a compound having a glass transition temperature of 100 ° C. or lower. The present invention has been completed by finding that the above problems can be solved.

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

<1>

A light-sensitive or radiation-sensitive resin composition containing a resin (A), a compound (B) having a glass transition temperature of 100 ° C. or lower, and a solvent.

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

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

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

The content of the compound (B) is 1% by mass or more with respect to the total solid content of the actinic cheilitis or radiation-sensitive resin composition.

A light-sensitive or radiation-sensitive resin composition having a solid content concentration of 10% by mass or more.

<2>

The sensitive light-sensitive or radiation-sensitive resin composition according to <1>, wherein the repeating unit (a1) is a repeating unit derived from a monomer having a glass transition temperature of 30 ° C. or lower when it is homopolymerized.

<3>

The actinic cheilitis or sensation according to <1> or <2>, wherein the repeating unit (a1) has a non-acidolytic alkyl group having 2 or more carbon atoms, which may contain a heteroatom in the chain. Radiation resin composition.

<4>

The actinic or radiation-sensitive resin composition according to <3>, wherein the repeating unit (a1) is a repeating unit represented by the following general formula (1-2).

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

<5>

The actinic or radiation-sensitive resin composition according to <1> or <2>, wherein the repeating unit (a1) is a repeating unit represented by the following general formula (1-3).

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

<6>

The actinic light-sensitive or radiation-sensitive resin composition according to any one of <1> to <5>, wherein the resin (A) contains a repeating unit (a4) having a phenolic hydroxyl group.

<7>

The actinic cheilitis or sensation according to any one of <1> to <6>, wherein the content of the repeating unit (a2) is 50 mol% or less with respect to all the repeating units of the resin (A). Radiation resin composition.

<8>

The sensitivity according to any one of <1> to <7>, wherein the content of the repeating unit (a2) is more than 19 mol% and 50 mol% or less with respect to all the repeating units of the resin (A). A light or radiation sensitive resin composition.

<9>

The item according to any one of <1> to <8>, wherein the content of the compound (B) is 20% by mass or less based on the total solid content of the actinic cheilitis or radiation-sensitive resin composition. A sensitive light-sensitive or radiation-sensitive resin composition.

<10>

The item according to any one of <1> to <9>, wherein the content of the compound (B) is 5 to 15% by mass with respect to the total solid content of the actinic cheilitis or radiation-sensitive resin composition. Sensitive light-sensitive or radiation-sensitive resin composition.

<11>

The actinic light-sensitive or radiation-sensitive resin composition according to any one of <1> to <10>, wherein the compound (B) is a resin.

<12>

The actinic light-sensitive or radiation-sensitive resin composition according to any one of <1> to <10>, wherein the compound (B) is a compound having a molecular weight of 100 to 5000.

<13>

The actinic or radiation-sensitive resin composition according to <11> or <12>, wherein the compound (B) is a non-ether compound.

<14>

A resist film formed of the actinic cheilitis or radiation-sensitive resin composition according to any one of <1> to <13>.

<15>

(I) A step of forming a sensitive light-sensitive or radiation-sensitive film on a substrate with a sensitive light-sensitive or radiation-sensitive resin composition.

(Ii) A step of irradiating the above-mentioned sensitive light or radiation sensitive film with active light or radiation, and

(Iii) A pattern forming method comprising a step of developing a sensitive light-sensitive or radiation-sensitive film irradiated with the above-mentioned active light beam or radiation using a developing solution.

The pattern forming method, wherein the sensitive light-sensitive or radiation-sensitive resin composition is the sensitive light-sensitive or radiation-sensitive resin composition according to any one of <1> to <13>.

<16>

A method for manufacturing an electronic device including the pattern forming method according to <15>.

According to the present invention, when a pattern is formed from a thick resist film (for example, having a thickness of 1 μm or more), the resolution of the unisolated pattern is excellent, and the development residue after development of the pattern can be reduced. A sensitive light-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method for manufacturing an electronic device, which are excellent in PCD performance and capable of suppressing roughness on the side wall of a pattern that may occur during etching. Can be provided.

Hereinafter, the present invention will be described in detail.

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

As used herein, the term "active light" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electrons. It means a line (EB: Electron Beam) or the like. As used herein, the term "light" means active light or radiation. Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, EUV, etc., but also electron beams and ions. It also includes drawing with particle beams such as beams.

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

As used herein, (meth) acrylate represents at least one of acrylate and methacrylate. Further, (meth) acrylic acid represents at least one of acrylic acid and methacrylic acid.

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

Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes a group having a substituent as well as a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the "organic group" in the present specification means a group containing at least one carbon atom.

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

(Substituent T)

Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy group such as methoxy group, ethoxy group and tert-butoxy group; aryloxy group such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and metoxalyl group and the like. Acrylic groups of: alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfonyl groups; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; Carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; Can be mentioned.

[Actinic cheilitis or radiation-sensitive resin composition]

The sensitive light-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also simply referred to as “the composition of the present invention”) comprises a resin (A), a compound (B) having a glass transition temperature of 100 ° C. or lower, and a compound (B). A sensitive light-sensitive or radiation-sensitive resin composition containing a solvent.

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

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

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

The content of the compound (B) is 1% by mass or more with respect to the total solid content of the actinic cheilitis or radiation-sensitive resin composition.

A light-sensitive or radiation-sensitive resin composition having a solid content concentration of 10% by mass or more.

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. Further, it may be a resist composition for alkaline development or a resist composition for organic solvent development. Of these, a positive resist composition is preferable, and a resist composition for alkaline development is preferable.

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

With the composition of the present invention, when a pattern is formed from a thick resist film (for example, having a thickness of 1 μm or more), the resolution of the isolated pattern is excellent, and the development residue after development of the pattern can be reduced. The reason why it is possible, excellent in PCD performance, and capable of suppressing roughness on the side wall of the pattern that may occur during etching has not been clarified in detail, but it is estimated as follows.

Since the resin (A) contained in the composition of the present invention has a repeating unit (a1) derived from a monomer having a glass transition temperature (Tg) of 50 ° C. or lower when homopolymerized, it is a highly flexible polymer. Is. Further, the compound (B) contained in the composition of the present invention is a compound having high flexibility because the Tg is 100 ° C. or lower. Since the quality of the resist film formed from the composition of the present invention containing these highly flexible materials becomes flexible, the internal stress that is remarkably generated in the case of a thick film is alleviated, and pattern peeling is suppressed. Therefore, it is considered that the resolution of the isolated pattern is improved.

Further, it is considered that the presence of the highly flexible polymer and the highly flexible compound makes it easier for the polymer to loosen during development and improves the solubility, thereby reducing the development residue.

Further, in general, when a resist composition containing a solvent is applied onto a substrate to form a resist film, a certain amount of solvent remains in the resist film. The residual solvent in the resist film gradually volatilizes and decreases with the passage of time, which affects the film quality. Since the resist film formed by using the composition of the present invention has a flexible film quality as described above, the residual solvent is more easily volatilized and removed than the conventional resist film, and the solvent remains in the resist film. It is thought that it is becoming difficult. As a result, it is considered that the PCD performance is improved because the change in the film quality is small and the CD fluctuation can be suppressed.

Further, it is considered that the flexibility of the resist film suppresses the generation of local irregularities during etching and suppresses the roughness on the side wall of the resist pattern.

<Resin (A)>

The resin (A) contained in the composition of the present invention has a repeating unit (a1) derived from a monomer having a glass transition temperature (Tg) of 50 ° C. or lower when homopolymerized, and an acid-degradable group. The repeating unit (a1) includes a repeating unit (a2), and the repeating unit (a1) is a non-acidolytic repeating unit. Further, the resin (A) has a repeating unit having an aromatic ring.

Since the resin (A) contains a repeating unit having an acid-decomposable group, it is a resin (acid-decomposable resin) whose polarity is increased by decomposing due to the action of an acid. That is, in the pattern forming method of the present invention described later, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer. A negative pattern is preferably formed in.

(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 homopolymerized.

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

(Method of measuring the glass transition temperature of homopolymer)

The glass transition temperature of the homopolymer is measured by the differential scanning calorimetry (DSC) method, if there is a catalog value or a literature value, if there is one. The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg is 18,000, and the dispersity (Mw / Mn) is 1.7. As the DSC apparatus, a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Co., Ltd. is used, and the temperature rise rate is measured at 10 ° C./min.

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

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

The monomer a1 is not particularly limited as long as the glass transition temperature (Tg) when homopolymerized is 50 ° C. or lower, and the resolution of the dot pattern is improved and the roughness on the side wall of the resist pattern that may occur during etching is increased. From the viewpoint of suppression, it is preferable that the Tg of the homopolymer is 30 ° C. or lower. The lower limit of Tg when the monomer a1 is homopolymer is not particularly limited, but is preferably −80 ° C. or higher, more preferably −70 ° C. or higher, still more preferably −60 ° C. or higher, and particularly preferably. Is -50 ° C or higher. It is preferable to set the lower limit of Tg when the monomer a1 is a homopolymer in the above range because the fluidity of the pattern during heating is suppressed and the verticality of the dot pattern is further improved.

The repeating unit (a1) is a repeating unit having a non-acidolytic alkyl group having 2 or more carbon atoms, which may contain a heteroatom in the chain in that the residual solvent can be more easily volatilized. Is preferable. As used herein, the term "non-acidic" means that the acid generated by the photoacid generator does not cause an elimination / decomposition reaction.

That is, more specifically, the "non-acid-degradable alkyl group" is an alkyl group that does not desorb from the resin (A) due to the action of the acid generated by the photoacid generator, or a photoacid generator. Examples thereof include alkyl groups that are not decomposed by the action of acid.

The non-acidolytic alkyl group may be linear or branched chain.

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

The non-acidolytic alkyl group having 2 or more carbon atoms which may contain a hetero atom in the chain is not particularly limited, but for example, an alkyl group having 2 to 20 carbon atoms and a hetero in the chain. Alkyl groups having 2 to 20 carbon atoms containing an atom can be mentioned.

As an alkyl group having 2 to 20 carbon atoms containing a heteroatom in the chain, for example, one or more -CH _2- is -O-, -S-, -CO-, -NR _6-. , Or an alkyl group substituted with a divalent organic group in which two or more of these are combined. The R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

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

The number of carbon atoms of the non-acidolytic 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, and more preferably 2 or more and 10 or less. It is more preferably 2 or more and 8 or less. The lower limit of the carbon number of the non-acid-decomposable alkyl group having 2 or more carbon atoms is preferably 4 or more.

The non-acidically 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).

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-acidolytic alkyl group having 2 or more carbon atoms, which may contain a heteroatom in the chain.

The _{halogen atom represented by R 1} is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The _{alkyl group represented by R 1} is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, and a tert-butyl group. .. Of these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.

The _{cycloalkyl group represented by R 1} is not particularly limited, and examples thereof include a cycloalkyl group having 5 to 10 carbon atoms, and more specifically, a cyclohexyl group and the like.

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

In the chain represented by R ₂ may contain a hetero atom, definitions and preferred aspects of two or more non-acid-decomposable alkyl group carbon atoms are as described above.

Further, the repeating unit (a1) may contain a heteroatom in the chain, and may be a non-acid-degradable alkyl group having a carboxy group or a hydroxyl group, or a ring member, in that the residual solvent can be more easily volatilized. It may be a repeating unit having a non-acidolytic cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom.

Hereinafter, a non-acidically decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in the chain, or a non-acidic decomposition having a carboxy group or a hydroxyl group, which may contain a heteroatom in a ring member. A repeating unit having a sex cycloalkyl group will be described.

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

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

The non-acidolytic alkyl group which may contain a hetero atom in the chain is not particularly limited, for example, an alkyl group having 2 to 20 carbon atoms and a carbon number containing a hetero atom in the chain. Examples include 2 to 20 alkyl groups. At least one of the hydrogen atoms in the alkyl group is substituted with a carboxy group or a hydroxyl group.

As an alkyl group having 2 to 20 carbon atoms containing a heteroatom in the chain, for example, one or more -CH _2- is -O-, -S-, -CO-, -NR _6-. , Or an alkyl group substituted with a divalent organic group in which two or more of these are combined. The R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The number of carbon atoms of the non-acid-decomposable alkyl group, which may contain a hetero atom in the chain, is preferably 2 to 16 and more preferably 2 to 10 in that it is more excellent in crack resistance (cracks are less likely to occur). 2 to 8 are preferable, and 2 to 8 are more preferable.

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

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

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

The non-acidolytic cycloalkyl group which may contain a heteroatom in the ring member is not particularly limited, for example, a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group), and a cycloalkyl group. , A cycloalkyl group having 5 to 20 carbon atoms containing a hetero atom in the ring member can be mentioned. At least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxy group or a hydroxyl group.

As a cycloalkyl group having 5 to 20 carbon atoms containing a hetero atom in the ring member, for example, one or more -CH ₂ − is −O−, −S−, −CO−, −NR ₆ -Or, a cycloalkyl group substituted with a divalent organic group obtained by combining two or more of these can be mentioned. The R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

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

A non-acidolytic alkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in the chain, or a non-acidolytic cyclo having a carboxy group or a hydroxyl group, which may contain a heteroatom in a ring member. As the repeating unit having an alkyl group, the repeating unit represented by the following general formula (1-3) is particularly preferable because it is more excellent in the effect of the present invention.

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

In the general formula (1-3), R ₃ has the _{same meaning as R 1} described above, and the preferred embodiment is also the same.

In the chain represented by R ₄ may contain a hetero atom, non-acid-decomposable group having a carboxy group or a hydroxyl group, or, in the ring members may include a hetero atom, a carboxyl group or a hydroxyl group The definition and preferred embodiment of the non-acidolytic cycloalkyl group having are as described above.

Among them, as R ₄ , a non-acid-degradable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the ring member, is preferable. Examples of this embodiment include a repeating unit having the following structure.

Examples of the monomer a1 include ethyl acrylate (-22 ° C.), n-propyl acrylate (-37 ° C.), isopropyl acrylate (-5 ° C.), n-butyl acrylate (-55 ° C.), and n-butyl methacrylate (20 ° C.). ), N-hexyl acrylate (-57 ° C), n-hexyl methacrylate (-5 ° C), n-octyl methacrylate (-20 ° C), 2-ethylhexyl acrylate (-70 ° C), isononyl acrylate (-70 ° C). 82 ° C.), Lauryl methacrylate (-65 ° C.), 2-Hydroxyethyl acrylate (-15 ° C.), 2-Hydroxypropyl methacrylate (26 ° C.), 1- [2- (methacryloyloxy) ethyl] succinate (9 ° C.) , 2-Ethylhexyl methacrylate (-10 ° C), sec-butyl acrylate (-26 ° C), methoxypolyethylene glycol monomethacrylate (n = 2) (-20 ° C), hexadecyl acrylate (35 ° C) and the like. .. In addition, the parentheses represent Tg (° C.) when homopolymer is used.

Methoxypolyethylene glycol monomethacrylate (n = 2) is a compound having the following structure.

Monomer a1 includes n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, hexadecyl acrylate, 2-hydroxyethyl acrylate, and the following. It is preferably a compound represented by MA-5.

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

In the resin (A), the content of the repeating unit (a1) (if there are a plurality of repeating units (a1), the total thereof) is preferably 5 mol% or more with respect to all the repeating units of the resin (A). 10 mol% or more is more preferable, 50 mol% or less is preferable, 40 mol% or less is more preferable, and 30 mol% or less is further preferable. Among them, the content of the repeating unit (a1) in the resin (A) (if there are a plurality of repeating units (a1), the total) is 5 to 50 mol% with respect to all the repeating units of the resin (A). Is preferable, 5 to 40 mol% is more preferable, and 5 to 30 mol% is further preferable.

(Repeating unit (a2))

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

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

In the resin (A), the content of the repeating unit (a2) (if there are a plurality of repeating units (a2), the total thereof) may be 50 mol% or less with respect to all the repeating units of the resin (A). It is preferably more than 19 mol% and more preferably 50 mol% or less. When the content of the repeating unit (a2) is 50 mol% or less, it is preferable from the viewpoint of improving the resolution of the dot pattern and reducing the development residue. When the content of the repeating unit (a2) is more than 19 mol%, the PCD performance is further improved, which is preferable.

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

Examples of the polar group include a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfo group, a sulfonyl amide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and a (alkylsulfonyl) (alkylcarbonyl) imide group. Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Examples thereof include an acidic group (a group that dissociates in a 2.38 mass% tetramethylammonium hydroxide aqueous solution) and an alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than the hydroxyl group directly bonded on the aromatic ring (phenolic hydroxyl group), and the α-position of the hydroxyl group is electron attraction such as a fluorine atom. Aromatic alcohols substituted with sex groups (eg, hexafluoroisopropanol groups, etc.) are excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

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

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

Examples of the group (leaving group) desorbed by the action of acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and-. Examples thereof include C (R ₀₁ ) (R ₀₂ ) (OR _39).

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 combined with each other to form a ring.

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

The alkyl groups of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ are preferably alkyl groups having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and hexyl. Groups, octyl groups and the like can be mentioned.

The cycloalkyl groups of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic.

The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic cycloalkyl group, a cycloalkyl group having 6 to 20 carbon atoms is preferable. Examples thereof include a tetracyclododecyl group and an androstanyl group. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

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

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

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

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

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

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

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

In the general formula (AI)

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

T represents a single bond or a divalent linking group.

Rx _{1 to Rx 3} independently represent an alkyl group or a cycloalkyl group.

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

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

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

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

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

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

The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and may be methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, An isobutyl group, a t-butyl group, or the like is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may have a part of the carbon-carbon bond as a double bond.

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

The _{ring structure formed by combining Rx 1} , Rx ₂ and Rx ₃ is a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, or a norbornane ring or a tetracyclo. Polycyclic cycloalkyl rings such as decane rings, tetracyclododecane rings, and adamantane rings are preferred. Of these, a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable. As _{the ring structure formed by combining Rx 1} , Rx ₂ and Rx ₃ , the structure shown below is also preferable.

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

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

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

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

The resin (A) preferably has, as a repeating unit having an acid-degradable group, a repeating unit having a structure protected by a leaving group in which a phenolic hydroxyl group is decomposed and eliminated by the action of an acid. In addition, in this specification, a phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

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

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

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

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

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

In the formulas (Y1) and (Y2), Rx _{1 to Rx 3} independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic). However, when _{all of Rx 1 to Rx 3} are alkyl groups (linear or branched chain), it is preferable that 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 each independently linear. It is more preferably a repeating unit representing an alkyl group.

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

As _{the alkyl group of Rx 1 to Rx 3} , an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group is preferable. ..

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

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

The _{cycloalkyl group formed by combining two of Rx 1 to Rx 3} is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.

The groups represented by the formulas (Y1) and (Y2) include, for example, an embodiment 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. 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 combined with each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like. R ₃₆ is preferably a hydrogen atom.

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

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

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

In the general formula (AII),

R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ may _{be bonded to Ar 6} to form a ring, in which case R ₆₂ represents a single bond or an alkylene group.

X ₆ represents a single bond, -COO-, or -CONR _64- . R ₆₄ represents a hydrogen atom or an alkyl group.

L ₆ represents a single bond or an alkylene group.

Ar ₆ represents an (n + 1) -valent aromatic hydrocarbon group, and represents an (n + 2) -valent aromatic hydrocarbon group when combined with _{R 62 to form a ring.}

Y ₂ represents a group desorbed by the action of a hydrogen atom or an acid independently when n ≧ 2. However, _{at least one of Y 2} represents a group that is eliminated by the action of an acid. The _{groups eliminated by the action of the acid as Y 2} are preferably of the formulas (Y1) to (Y4).

n represents an integer of 1 to 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 the like. Examples thereof include an alkoxycarbonyl group (2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferable.

(Other repeating units)

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

The other repeating units that the resin (A) can contain will be described in detail below.

(Repeating unit having a carboxy group (a3))

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

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

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

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

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

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

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

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

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

During the ceremony

R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may _{be bonded to Ar 4} to form a ring, in which case R ₄₂ represents a single bond or an alkylene group.

X ₄ represents a single bond, -COO-, or -CONR _64- , and R ₆₄ represents a hydrogen atom or an alkyl group.

L ₄ represents a single bond or a divalent linking group.

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

n represents an integer of 1 to 5.

For the purpose of increasing the polarity of the repeating unit represented by the general formula (I), it is also preferable that _{n is an integer of 2 or more, or X 4} is -COO- or -CONR _64-.

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

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

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

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

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

Ar ₄ represents an (n + 1) -valent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group when n is 1 may have a substituent, for example, an arylene having 6 to 18 carbon atoms such as a phenylene group, a trilene group, a naphthylene group, and an anthracenylene group. A group or an aromatic hydrocarbon group containing a heterocycle such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazol, and thiazole is preferred.

As a specific example of the (n + 1) -valent aromatic hydrocarbon group when n is an integer of 2 or more, (n-1) arbitrary number of (n-1) valent aromatic hydrocarbon groups from the above-mentioned specific example of the divalent aromatic hydrocarbon group A group formed by removing a hydrogen atom can be preferably mentioned.

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

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

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

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

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

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

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

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

In the resin (A), the content of the repeating unit (a4) is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, based on all the repeating units in the resin (A). preferable. The content of the repeating unit (a4) is preferably 85 mol% or less, more preferably 80 mol% or less, based on all the repeating units in the resin (A).

(Repeating unit (a5))

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

The lactone structure or sultone structure may have a lactone structure or a sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable. Among them, a 5- to 7-membered ring lactone structure in which another ring structure is fused to form a bicyclo structure or a spiro structure, or a 5 to 7-membered ring in the form of a bicyclo structure or a spiro structure. A sultone structure in which another ring structure is fused is more preferable.

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

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

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

In the above general formula (III),

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

n is the _{number of repetitions of the structure represented by −R 0} −Z−, represents an integer of 0 to 5, is preferably 0 or 1, and more preferably 0. When n is 0, −R ₀ −Z− does not exist and a single bond is formed.

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

Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are a plurality of Z's, each of them independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.

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

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

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

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

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

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

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

n represents an integer greater than or equal to 0.

_RA ² represents a substituent. When n is 2 or more, _RA ² independently represents a substituent.

A represents a single bond or a divalent linking group.

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

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

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

Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and the specific example of the monomer corresponding to the repeating unit represented by the general formula (A-1) will be given. It is not limited to these specific examples. The following specific examples, which _R ^{A 1} in _{R 7} and formula in the formula (III) (A-1) is equivalent to the case is a methyl group, _{R 7} and _R ^{A 1} represents a hydrogen atom, a halogen atom , Or can be optionally substituted with a monovalent organic group.

In addition to the above-mentioned monomers, the following monomers are also preferably used as raw materials for the resin (A).

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

In addition to the above-mentioned repeating structural units, the resin (A) has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or, as well as general necessary characteristics of resist, such as resolving power, heat resistance, and sensitivity. It may have various repeating structural units for the purpose of adjusting.

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

The predetermined monomer has one addition-polymerizable unsaturated bond selected from, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. Examples include compounds.

In addition, an addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the various repeating structural units may be used.

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

(Repeating unit with aromatic ring)

The resin (A) is a repeating unit in which at least one of the repeating units in the resin (A) has an aromatic ring.

In the resin (A), the content of the repeating unit having an aromatic ring is, for example, 40 mol% or more and 55 mol% with respect to all the repeating units in the resin (A) in that it is superior in etching resistance. The above is preferable, and 60 mol% or more is more preferable. The upper limit thereof 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))

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

Examples of the reaction solvent during polymerization include ethers such as tetrahydrofuran, 1,4-dioxane, and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethylformamide, and dimethyl. Examples thereof include amides such as acetoamide, and solvents for dissolving the composition of the present invention such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and cyclohexanone, which will be described later. As the reaction solvent at the time of polymerization, it is preferable to use the same solvent as the solvent used in the composition of the present invention. As a result, the generation of particles during storage can be suppressed.

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

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

The weight average molecular weight of the resin (A) is preferably 1000 to 20000, more preferably 2000 to 30000, and even more preferably 3000 to 25000. The dispersity (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further 1.1 to 2.0. preferable.

The resin (A) may be used alone or in combination of two or more.

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

(Solid content concentration)

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

<Compound (B) with a glass transition temperature of 100 ° C or less>

The composition of the present invention contains a compound (B) having a glass transition temperature (Tg) of 100 ° C. or lower (also simply referred to as “compound (B)”).

The compound (B) is not particularly limited as long as it is a compound having a Tg of 100 ° C. or lower.

The compound (B) may be a polymer compound, an oligomer, or a low molecular weight compound.

As will be described later, the compound (B) is preferably a non-ether compound. By using a non-polyester compound as the compound (B), the adhesion of the resin (A) to the substrate is improved, and the resolution of the dot pattern is further improved.

It is preferable that compound (B) is not an acid diffusion control agent.

It is preferred that compound (B) is not a surfactant.

Compound (B) may be used alone or in combination of two or more.

The Tg of compound (B) is measured by a differential scanning calorimetry (DSC) method. As the DSC apparatus, a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Co., Ltd. is used, and the temperature rise rate is measured at 10 ° C./min.

A resin can be mentioned as a preferable embodiment of the compound (B).

The resin as compound (B) is also referred to as "resin (BI)".

The weight average molecular weight (Mw) of the resin (BI) is preferably 5,000 to 100,000, more preferably 6,000 to 50,000, further preferably 7,000 to 30,000, and particularly preferably 8,000 to 18,000. It is preferably 9000 to 17000, more preferably 1000 to 16000, and most preferably 1000 to 16000.

The dispersity (molecular weight distribution) of the resin (BI) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and 1.1 to 2 .0 is even more preferred.

The resin (BI) is not particularly limited, and examples thereof include polyvinyl butyral, polyvinyl methyl ether, polyester, polyether, polyester ether, polyester urethane, epoxy resin, and novolak resin. For example, polyesters and / or polyethers described in JP-A-2002-29256, polyester ethers described in JP-A-5-97073, polyester urethanes or polyesters, copolyester ethers described in JP-A-2-292342, Examples thereof include epoxy resins and novolak resins described in JP-A-2002-146404.

Further, as the resin (BI), a resin having the repeating unit mentioned in the resin (A) may be used.

The content of the repeating unit having a phenolic hydroxyl group in the resin (BI) is preferably 53 mol% or less, more preferably 50 mol% or less, based on all the repeating units of the resin (BI).

When the resin (BI) has a repeating unit having a phenolic hydroxyl group, the content thereof is preferably 10 mol% or more, more preferably 20 mol% or more, based on all the repeating units of the resin (BI). preferable.

The resin (BI) preferably has a repeating unit derived from hydroxystyrene as the repeating unit having a phenolic hydroxyl group.

The compound (B) is preferably a non-ether compound. That is, the resin (BI) is preferably non-polyester.

Another preferred embodiment of compound (B) is a compound having a molecular weight of 100 to 5000.

A compound having a molecular weight of 100 to 5000 as compound (B) is also referred to as "compound (BII)".

The molecular weight of compound (BII) is preferably 100 to 4000, more preferably 150 to 3000, and most preferably 200 to 2000.

The compound (BII) is not particularly limited, and examples thereof include a polyether compound, a phosphoric acid ester, a carboxylic acid ester, a polyol ester, and a sulfonic acid ester.

A polyether compound is a compound having two or more ether bonds.

Examples of the polyether compound include compounds having a partial structure represented by the following general formula (BP-1).

In the general formula ^{(BP-1), R P1} represents an alkylene group. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 15, more preferably 2 to 8, and even more preferably 2. The alkylene group may have a substituent, and the substituent is not particularly limited, but is preferably an alkyl group (preferably having 1 to 10 carbon atoms).

In the above general formula (BP-1), m1 represents an integer of 2 or more. Of these, it is preferably an integer of 2 to 20. A plurality of ^RP1s may be the same or different. The average value of m1 is preferably 2 to 25, more preferably 2 to 10, and even more preferably 4 to 8.

In the above general formula (BP-1), * represents a bond.

The compound having a partial structure represented by the general formula (BP-1) is preferably a compound represented by the following general formula (BP-2) or the following general formula (BP-3).

Definition of ^{R P1} in the general formula (BP-2), specific examples and preferred embodiments are the same as ^{R P1} in general formula (BP-1).

In the above general formula (BP-2), ^RP2 and ^RP3 each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 15.

In the above general formula (BP-2), m1 represents an integer of 2 or more. m1 is preferably an integer of 2 to 20, and more preferably 10 or less. A plurality of ^RP1s may be the same or different. The upper limit of the average value of m1 is preferably 25 or less, more preferably 20 or less, further preferably 10 or less, particularly preferably 8 or less, and most preferably 6 or less. preferable. The lower limit of m1 is preferably 2 or more, and more preferably 4 or more. More specifically, the average value of m1 is preferably 2 to 25, more preferably 2 to 15, further preferably 2 to 8, and particularly preferably 4 to 8. Most preferably, it is 4 to 6.

Definition of ^{R P1} in the general formula (BP-3), specific examples and preferred embodiments are the same as ^{R P1} in general formula (BP-1).

The definition and preferred embodiment of m1 in the general formula (BP-3) is the same as m1 in the general formula (BP-2) described above.

Examples of the compound represented by the above general formula (BP-3) include crown ether.

The compound (BII) is preferably a polyether compound having a group represented by the following general formula (BP-4).

As a result, when the resist pattern obtained from the thick resist film (for example, having a thickness of 1 μm or more) is measured in the vacuum chamber of the length measuring SEM, cracks are less likely to occur. As a result, the performance evaluation of the resist pattern can be performed more accurately.

上記一般式（ＢＰ−４）中、Ｒ^Ｐ４はアルキレン基を表す。複数のＲ^Ｐ４は、互いに同一であっても、異なっていてもよい。ｍ２は２以上の整数を示す。＊は、結合手を表す。

In the above general formula (BP-4), ^RP4 represents an alkylene group. The plurality of ^RP4s may be the same as or different from each other. m2 represents an integer of 2 or more. * Represents a bond.

Specific examples and preferred embodiments of ^{R P4} and m2 in formula (BP-4), respectively, are the same as those described for ^{R P1} and m1 in formula (BP-1).

The polyether compound having a group represented by the general formula (BP-4) may have one group represented by the general formula (BP-4) or two or more groups. good.

The polyether compound having a group represented by the general formula (BP-4) is preferably a polyether compound represented by the following general formula (BP-5).

In the general formula (BP-5), ^RP4 and m2 are synonymous with those in the general formula (BP-4).

^RP5 represents a hydrogen atom or a hydroxyl group.

R ^P5 is preferably a hydroxyl group.

The boiling point of the polyether compound having a group represented by the general formula (BP-4) is preferably 220 ° C. or higher, more preferably 300 ° C. or higher, still more preferably 350 ° C. or higher. ..

The boiling point of the polyether compound having a group represented by the general formula (BP-4) is typically 550 ° C. or lower.

The ClogP value of the polyether compound having a group represented by the general formula (BP-4) is preferably -2.5 to -0.3, preferably -2.5 to -0.5. It is more preferable that there is, and it is further preferable that it is −2.5 to −1.0.

Here, the ClogP value is a ClogP value of a monomer (compound having an unsaturated double bond group) corresponding to a repeating unit, and is described in Chem DrawUltra ver. It is a value calculated by 12.0.2.10.76 (Cambridge Corporation).

As described above, when the polyether compound having a group represented by the general formula (BP-4) satisfies the above-mentioned preferable range of boiling point and the above-mentioned preferable range of ClogP value, cracks are less likely to occur. The effect tends to be more easily obtained.

In a preferred embodiment of the present invention, the polyether compound having a group represented by the general formula (BP-4) is a compound represented by the general formula (BP-5) and is represented by the general formula (BP-5). ^{R P5} at -5) is a hydroxyl group, a compound having a boiling point of 350 ° C. or higher.

The molecular weight of the polyether compound is not particularly limited, but is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 2000.

It is preferable that the polyether compound does not contain a basic moiety (for example, an amino group or a proton acceptor functional group described later).

The pKa of the conjugate acid of the polyether compound is preferably 0 or less, more preferably -1 or less, further preferably -2 or less, and particularly preferably -3 or less. The lower limit of pKa is, for example, -15 or more.

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

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

It is preferable that the polyether compound does not have a functional group having a nitrogen atom having a lone electron pair with a small contribution of π conjugation. Examples of the nitrogen atom having an isolated electron pair having a small contribution of π-conjugation include a nitrogen atom having a partial structure shown in the following general formula. Examples of the structure (compound) having a functional group having a nitrogen atom having an isolated electron pair having a small contribution of π-conjugation include chain amides, cyclic amides, aromatic amines, chain aliphatic amines and cyclic fats. Group amines can be mentioned.

Specific examples of the polyether compounds will be given below, but the present invention is not limited thereto.

The compound (BII) is preferably a non-ether compound, more preferably a phosphoric acid ester, a carboxylic acid ester, a polyol ester, or a sulfonic acid ester.

When compound (BII) is a phosphate ester, examples of phosphate esters include triphenyl phosphate (TPP), tricresyl phosphate, cresil diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, Includes tributyl phosphate and the like.

When compound (BII) is a carboxylic acid ester, phthalates and citric acid esters are typical examples of carboxylic acid esters. Examples of phthalates include dimethylphthalate, diethylphthalate, dibutylphthalate, dioctylphthalate, diphenylphthalate, diethylhexylphthalate and the like. Examples of citric acid esters include triethyl O-acetylcitrate, tributyl O-acetylcitrate, acetyltriethyl citrate, acetyltributyl citrate and the like.

Examples of other carboxylic acid esters include butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Examples of glycolic acid esters include triacetin, tributyrin, butylphthalylbutylglycolate, ethylphthalylethylglycolate, methylphthalylethylglycolate, butylphthalylbutylglycolate, methylphthalylmethylglycolate, and propylphthalyl. There are propyl glycolate, butylphthalylbutylglycolate, octylphthalyloctylglycolate and the like.

Further, examples of carboxylic acid esters include 1,6-hexanediol diacetate, 1,2-butanediol diacetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, and 1,5-. Examples thereof include pentandiol diacetate and DL-diethyl appleate.

Further, JP-A-5-194788, JP-A-60-250053, JP-A-4-227941, JP-A-6-16869, JP-A-5-271471 and JP-A-7-286068. , JP-A-5-5047, JP-A-11-80381, JP-A-7-20317, JP-A-8-57879, JP-A-10-152568, JP-A-10-12824. Compounds described in publications and the like are also preferably used.

In addition, (di) pentaerythritol esters described in JP-A-11-124445, glycerol esters described in JP-A-11-246704, diglycerol esters described in JP-A-2000-63560, JP-A-11- Citrate esters described in Japanese Patent Application Laid-Open No. 92574, substituted phenyl phosphate esters described in JP-A-11-909946, ester compounds containing an aromatic ring and a cyclohexane ring described in JP-A-2003-165868, etc. are preferably used. Be done.

When the compound (BII) is a carboxylic acid ester, the compound (BII) preferably has 2 to 6 ester bonds, more preferably 2 to 4, and particularly preferably 2 ester bonds.

When the compound (BII) is a carboxylic acid ester, the molecular weight of the compound (BII) is preferably 100 to 1000, more preferably 100 to 700, and further preferably 100 to 400. preferable.

When the compound (BII) is a sulfonic acid ester, examples of the sulfonic acid ester include butyl p-toluenesulfonic acid, hexyl p-toluenesulfonic acid, octyl p-toluenesulfonic acid, and phenylcresyl ester of pentadecylsulfonic acid. Is included.

Specific examples of the case where the compound (BII) is a non-ether compound are shown below, but the present invention is not limited thereto.

As described above, the glass transition temperature of compound (B) is 100 ° C. or lower.

When the compound (B) is a resin, its glass transition temperature is preferably −50 ° C. or higher, more preferably −20 ° C. or higher, and even more preferably 0 ° C. or higher.

When the compound (B) is not a resin (polymer), its glass transition temperature is preferably −20 ° C. or higher, and preferably −15 ° C. or higher. In this case, the glass transition temperature of compound (B) is usually 50 ° C. or lower.

The method for measuring the glass transition temperature is as described above.

The compound (B) is not particularly limited as long as the glass transition temperature is 100 ° C. or lower, and when such a compound is a resin, as described above, the repeating unit that the resin (BI) may have is a repeating unit. It can be preferably obtained by setting the content, weight average molecular weight, etc. within the above-mentioned suitable range, and when the compound (B) is not a resin, by appropriately selecting the type of the compound.

In the composition of the present invention, the content of the compound (B) is 1% by mass or more with respect to the total solid content of the composition from the viewpoint of PCD performance and suppression of roughness on the side wall of the pattern that may occur during etching. , 20% by mass or less, more preferably 5 to 15% by mass.

<Solvent>

The composition of the present invention contains a solvent.

In the composition of the present invention, a known resist solvent can be appropriately used as the solvent. For example, paragraphs <0665> to <0670> of US Patent Application Publication 2016/0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication 2015/0004544A1, US Patent Application Publication 2016/0237190A1. Known solvents disclosed in paragraphs <0424> to <0426> of the specification and paragraphs <0357> to <0366> of US Patent Application Publication No. 2016/0274458A1 can be preferably used.

Examples of the solvent that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionate, and cyclic lactone (preferably having 4 to 10 carbon atoms). Examples thereof include organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used may be used.

As the solvent having a hydroxyl group and the solvent having no hydroxyl group, the above-mentioned exemplified compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether (propylene glycol monomethyl ether). PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. Further, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene Glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, Cyclohexanone, cyclopentanone or 2-heptanone are more preferred. Propylene carbonate is also preferable as the solvent having no hydroxyl group.

The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. preferable. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in terms of coating uniformity.

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

<Compounds that generate acid when irradiated with active light or radiation>

The composition of the present invention preferably contains a compound (photoacid generator) that generates an acid when irradiated with active light or radiation.

As the photoacid generator, a compound that generates an organic acid by irradiation with active light or radiation is preferable. Examples thereof include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.

As the photoacid generator, a known compound that generates an acid by irradiation with active light or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs <0125> to <0319> of U.S. Patent Application Publication 2016/0070167A1, paragraphs <0083> to <0094> of U.S. Patent Application Publication 2015/0004544A1, and U.S. Patent Application Publication 2016 / The known compounds disclosed in paragraphs <0323> to <0402> of 0237190A1 can be preferably used.

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

In the above general formula (ZI)

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

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

Further, 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. The two of the group formed by bonding of the R ₂₀₁ to R _203, an alkylene group (e.g., butylene, pentylene) and _{-CH 2 -CH 2 -O-CH 2} -CH 2 - and the like.

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

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

The photoacid generator may be a compound having a plurality of structures represented by the general formula (ZI). _{For example, at least one of the compounds R 201 to} R ₂₀₃ represented by the general formula (ZI) and at least one of the other compounds R _{201 to} R ₂₀₃ represented by the general formula (ZI) are single-bonded. Alternatively, it may be a compound having a structure bonded via a linking group.

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

The compound (ZI-1) is an _{aryl sulfonium compound in which at least one of R 201 to} R ₂₀₃ of the above general formula (ZI) is an aryl group, that is, a compound having an aryl sulfonium as a cation.

In the aryl sulfonium compound _{, all of R 201 to} R ₂₀₃ may be an aryl group, or _{a part of R 201 to} R ₂₀₃ may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.

Examples of the aryl sulfonium compound include a triaryl sulfonium compound, a diallyl alkyl sulfonium compound, an aryl dialkyl sulfonium compound, a diallyl cycloalkyl sulfonium compound, and an aryl dicycloalkyl sulfonium compound.

As the aryl group contained in the aryl sulfonium compound, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues and the like. When the aryl sulfonium 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 contained in the arylsulfonium compound as required is a linear alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms. Cycloalkyl group is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ are independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group (for example, carbon number). It may have an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

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

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

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

R _{201 to} R ₂₀₃ are independently, preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group or 2-oxocyclo. It is an alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, etc.). Propyl group, butyl group, and pentyl group), and cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group).

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

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

In the general formula (ZI-3), M represents an alkyl group, a cycloalkyl group, or an aryl group, and when it has a ring structure, the ring structure includes an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon. -May contain at least one carbon double bond. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R _6c and R _7c may be combined to form a ring. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group. R _x and R _y may be combined to form a ring. Further, 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 represented by M and the cycloalkyl group include a linear alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms) and 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms). A branched chain alkyl group having 3 to 10) carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms) is preferable, and specifically, a methyl group, an ethyl group, or a propyl group. , N-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, norbornyl group and the like.

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

The M may further have a substituent (for example, a substituent T). Examples of this embodiment include a benzyl group as M.

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

_Examples of the alkyl group, cycloalkyl group, and aryl group represented by R _6c and R 7c include those similar to those of M described above, and the preferred embodiments thereof are also the same. Further, R _6c and R _7c may be combined to form a ring.

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

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

As the _{alkenyl group represented by R x} and R _y , an allyl group or a vinyl group is preferable.

The R _x and R _y may further have a substituent (for example, a substituent T). Examples of this embodiment include a 2-oxoalkyl group or an alkoxycarbonylalkyl group as _{R x} and R _y.

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

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

The _{ring structure formed by connecting R x} and R _y to each other may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.

In 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.

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

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

In the general formula (ZI-3A),

R _{1c to} R _5c are independently hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group. , Nitro group, alkylthio group or arylthio group.

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

R _x and R _{y are synonymous with R x} and R _y in the above-mentioned general formula (ZI-3), and the preferred embodiments thereof are also the same.

Any two or more of R _{1c to} R _{5c , R x} and R _y, may be bonded to each other to form a ring structure, and the ring structures are independently formed by an oxygen atom, a sulfur atom, and an ester bond. It may contain an amide bond or a carbon-carbon double bond. Further, R _5c and R _6c , R _5c and R _x may be bonded to each other to form a ring structure, and the ring structure may independently contain a carbon-carbon double bond. Further, R _6c and R _7c may be combined with each other to form a ring structure.

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

Examples of the group formed by combining any two or more of R _{1c to R 5c , R 6c} and R _7c , and R _x and R _y include a butylene group and a pentylene group.

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

Zc ⁻ represents an anion.

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

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

In the general formula (ZI-4),

l represents an integer from 0 to 2.

r represents an integer from 0 to 8.

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

When _{there are a plurality of R 14} , each of them is an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a monocyclic or polycyclic cycloalkyl. Represents an alkoxy group having a skeleton. These groups may have substituents.

R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have substituents. Bonded to two R ₁₅ each other may form a ring.

When two R ₁₅ are combined to form a ring together, in the ring skeleton may contain a hetero atom such as an oxygen atom, or a nitrogen atom. In one embodiment, two R ₁₅ is an alkylene group, it is preferable 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 chain. The alkyl group preferably has 1 to 10 carbon atoms. As the alkyl group, a methyl group, an ethyl group, an n-butyl group, a t-butyl group and the like are more preferable.

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

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

As _{the aryl group of R 204 to} R _207, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group of R _{204 to} R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

Examples of the alkyl group and cycloalkyl group of R _{204 to} R ₂₀₇ include a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, etc.). A butyl group and a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) are preferable.

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

Z ⁻ represents an anion.

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

In general formula (3),

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

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

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xfs are fluorine atoms.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. If R ₄ and _{R 5} there are a plurality, _{R 4} and _{R 5} may each be the same or different.

The _{alkyl group represented by R 4} and R ₅ may have a substituent and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are preferably 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's, the L's may be the same or different.

Examples of the divalent linking group include -COO- (-C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-,-. SO −, −SO ₂ −, alkylene group (preferably 1 to 6 carbon atoms), cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene group (preferably 2 to 6 carbon atoms), and a combination thereof. Divalent linking groups and the like can be mentioned. Among them, -COO -, - OCO -, - CONH -, - NHCO -, - CO -, - O -, - SO 2 -, - COO- alkylene group -, - OCO- alkylene group -, - CONH- alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.

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

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

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

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

The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can suppress the diffusion of acid more. Further, the heterocyclic group may or may not have aromaticity. Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the non-aromatic heterocycle include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above-mentioned resin. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms) and a cycloalkyl group (monocyclic, polycyclic, and spiroring). Any of them may be used, and the number of carbon atoms is preferably 3 to 20), an aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group and a sulfonamide. Groups and sulfonic acid ester groups can be mentioned. The carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be a carbonyl carbon.

Formula (3) As the anion represented ^{_{by, SO 3 - -CF 2 -CH 2}} -OCO- (L) q'-W, SO 3 - -CF 2 -CHF-CH 2 -OCO- (L) q'-W, SO ₃ ⁻ −CF ₂ −COO− (L) q'−W, SO ₃ ⁻ −CF ₂ −CF ₂ −CH ₂ −CH ₂ − (L) q−W, SO ₃ ⁻ −CF _2- CH (CF ₃ ) -OCO- (L) q'-W is preferable. Here, L, q and W are the same as in the general formula (3). q'represents an integer from 0 to 10.

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

In general formula (4),

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

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

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

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

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

In formula (SA1),

Ar represents an aryl group and may further have a substituent other than the sulfonic acid anion and the − (DB) group. Further, examples of the substituent which may be possessed include a fluorine atom and a hydroxyl group.

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

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

B represents a hydrocarbon group.

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

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

Formula (ZI), the general formula (ZII) anions in Z ^-, in the general formula (ZI-3) Z ^-, in the general formula (ZI-3A) Zc ^-, and in the Z formula (ZI-4) ^- of Preferred examples are shown below.

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

The photoacid generator may be in the form of a small molecule compound or may be incorporated in a part of the polymer. Further, the form of the small molecule compound and the form incorporated in a part of the polymer may be used in combination.

The photoacid generator is preferably in the form of a small molecule compound.

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

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

The photoacid generator may be used alone or in combination of two or more.

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

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

<Acid diffusion control agent>

The composition of the present invention preferably contains an acid diffusion control agent. The acid diffusion control agent acts as a quencher that traps the acid generated from the photoacid generator or the like during exposure and suppresses the reaction of the acid-degradable resin in the unexposed portion due to the excess generated acid. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation, an onium salt (DC) which is a weak acid relative to an acid generator, and a nitrogen atom. A low molecular weight compound (DD) having a group having a group desorbed by the action of an acid, an onium salt compound (DE) having a nitrogen atom in the cation portion, or the like can be used as an acid diffusion control agent. In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs <0627> to <0664> of US Patent Application Publication 2016/0070167A1, paragraphs <0995> to <0187> of US Patent Application Publication 2015/0004544A1, US Patent Application Publication 2016/0237190A1. Known compounds disclosed in paragraphs <0403> to <0423> of the specification and paragraphs <0259> to <0328> of US Patent Application Publication No. 2016/0274458A1 can be suitably used as the acid diffusion control agent. ..

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

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

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

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

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

Regarding the above alkyl group, as the alkyl group having a substituent, 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 is preferable.

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

As the basic compound (DA), guanidine, aminopyrrolidin, pyrazole, pyrazoline, piperazin, aminomorpholine, aminoalkylmorpholin, piperidine and the like are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, etc. A compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like are more preferable.

A basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation (hereinafter, also referred to as “compound (DB)”) has a proton acceptor functional group and is active light or It is a compound that is decomposed by irradiation with radiation to reduce or disappear its proton accepting property, or to change from proton accepting property to acidic.

A proton acceptor functional group is a functional group having a group or an electron that can electrostatically interact with a proton, and is, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π-conjugated group. Means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza-crown ether structure, a 1-3-grade amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.

The compound (DB) is decomposed by irradiation with active light or radiation to reduce or eliminate the proton acceptor property, or generate a compound in which the proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group, and is specific. Means that when a proton adduct is formed from a compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.

Proton acceptability can be confirmed by measuring pH.

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

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

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

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

When a photoacid generator and an onium salt that generates an acid that is relatively weak to the acid generated from the photoacid generator are mixed and used, the photoacid generator is activated by active light or by irradiation with radiation. When the acid generated from the above collides with an onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange to form an onium salt having a strong acid anion. In this process, the strong acid is exchanged for the weak acid having a lower catalytic ability, so that the acid is apparently inactivated and the acid diffusion can be controlled.

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

In the formula, R ⁵¹ represents a hydrocarbon group, Z ^2c represents a hydrocarbon group, R ⁵² represents an organic group, Y ³ represents an alkylene group, a cycloalkylene group or an arylene group, and Rf contains a fluorine atom. Representing a hydrocarbon group, M ⁺ independently represents an ammonium cation, a sulfonium cation or an iodonium cation.

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

Z ^2c preferably represents a hydrocarbon group having 1 to 30 carbon atoms.

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

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

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

The onium salt (DC), which is a weak acid relative to the photoacid generator, is a compound that has a cation moiety and an anion moiety in the same molecule, and the cation moiety and anion moiety are linked by a covalent bond. Hereinafter, it may also be referred to as “compound (DCA)”).

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

In the general formulas (C-1) to (C-3),

R ₁ , R ₂ , and R ₃ each independently represent a substituent having one or more carbon atoms.

L ₁ represents a divalent linking group or single bond that links the cation site and the anion site.

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

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

Substituents having 1 or more carbon atoms in R _{1 to} R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino. Examples thereof include a carbonyl group and an arylaminocarbonyl group. It is preferably an alkyl group, a cycloalkyl group, or an aryl group.

_{L 1} as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and 2 of these. Examples include groups made up of a combination of seeds and above. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

A small molecule compound (DD) having a nitrogen atom and having a group desorbed by the action of an acid (hereinafter, also referred to as "compound (DD)") has a group desorbed by the action of an acid on the nitrogen atom. It is preferably an amine derivative having.

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

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

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

In the general formula (d-1)

Rb is independently a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), and an aralkyl group (preferably 3 to 30 carbon atoms). It preferably represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be coupled to each other to form a ring.

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

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

Examples of the ring formed by connecting the two Rbs to each other include an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon and a derivative thereof.

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

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

In the general formula (6)

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

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

Rb is synonymous with Rb in the above general formula (d-1), and the same applies to preferred examples.

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

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra (these groups may be substituted with the above groups) include groups similar to the above-mentioned specific examples for Rb. Be done.

Specific examples of a particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph <0475> of U.S. Patent Application Publication No. 2012/01335348A1.

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter, also referred to as “compound (DE)”) is preferably a compound having a basic moiety containing a nitrogen atom in the cation portion. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is more preferable that all the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-attracting functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly linked to the nitrogen atom.

Preferred specific examples of the compound (DE) include, but are not limited to, the compound disclosed in paragraph <0203> of US Patent Application Publication 2015/0309408A1.

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

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 (the total of a plurality of types, if present) is preferably 0.05 to 10% by mass, preferably 0.05 to 10% by mass, based on the total solid content of the composition. 5% by mass is more preferable.

<Hydrophobic resin>

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

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

Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily have to have hydrophilic groups in the molecule, and polar / non-polar substances are uniformly mixed. It does not have to contribute to doing so.

The hydrophobic resin is at least one selected from the group consisting of _{"fluorine atoms", "silicon atoms", and "CH three-} part structure contained in the side chain portion of the resin" from the viewpoint of uneven distribution on the surface layer of the film. It is preferably a resin having a repeating unit having seeds.

When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin may be contained in the main chain of the resin and may be contained in the side chain. You may.

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

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

(X) Acid group

(Y) A group that decomposes due to the action of an alkaline developer and increases its solubility in an alkaline developer (hereinafter, also referred to as a polarity converting group).

(Z) A group that decomposes by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonyl group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkyl). Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) ) Methylene groups and the like can be mentioned.

As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis (alkylcarbonyl) methylene group is preferable.

Examples of the group (y) that decomposes due to the action of the alkaline developing solution and increases the solubility in the alkaline developing solution include a lactone group, a carboxylic acid ester group (-COO-), and an acid anhydride group (-C (O) OC). (O)-), acidimide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate ester group (-OC (O) O-), sulfate ester group (-OSO ₂ O-), and Examples thereof include a sulfonic acid ester group (-SO ₂ O-), and a lactone group or a carboxylic acid ester group (-COO-) is preferable.

Examples of the repeating unit containing these groups include a repeating unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include a repeating unit made of an acrylic acid ester and a methacrylic acid ester. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced into the end of the resin by using a polymerization initiator or chain transfer agent having these groups at the time of polymerization.

Examples of the repeating unit having a lactone group include the same repeating units having the lactone structure described above in the section of resin (A).

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

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

The hydrophobic resin may further have a repeating unit different from the repeating unit described above.

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

On the other hand, especially in the case where the hydrophobic resin comprises a CH ₃ partial structure side chain moiety, a hydrophobic resin is also preferable that is substantially free of fluorine atom and a silicon atom. Further, it is preferable that the hydrophobic resin is substantially composed of only 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, more preferably 1,000 to 50,000.

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

As the hydrophobic resin, a known resin can be appropriately selected and used alone or as a mixture thereof. For example, known resins disclosed in paragraphs <0451> to <0704> of U.S. Patent Application Publication 2015/016830A1 and paragraphs <0340> to <0356> of U.S. Patent Application Publication 2016/0274458A1. Can be suitably used as a hydrophobic resin. Further, the repeating unit disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190A1 is also preferable as the repeating unit constituting the hydrophobic resin.

A preferred example of the monomer corresponding to the repeating unit constituting the hydrophobic resin is shown below.

The hydrophobic resin may be used alone or in combination of two or more.

It is preferable to mix and use two or more kinds of hydrophobic resins having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure.

The content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention.

<Crosslinking agent (G)>

The composition of the present invention may contain a compound (hereinafter, also referred to as a cross-linking agent (G)) that cross-links the resin by the action of an acid. As the cross-linking agent (G), a known compound can be appropriately used. For example, known compounds disclosed in paragraphs <0379> to <0431> of U.S. Patent Application Publication 2016 / 0147154A1 and paragraphs <0064> to <0141> of U.S. Patent Application Publication 2016/0282720A1. Can be suitably used as a cross-linking agent (G).

The cross-linking agent (G) is a compound having a cross-linking group capable of cross-linking the resin, and examples of the cross-linking group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, and an oxylan ring. And the oxetane ring and the like.

The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxylan ring or an oxetane ring.

The cross-linking agent (G) is preferably a compound (including a resin) having two or more cross-linking groups.

The cross-linking agent (G) is more preferably a phenol derivative, a urea-based compound (compound having a urea structure) or a melamine-based compound (a compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.

The cross-linking agent may be used alone or in combination of two or more.

The content of the cross-linking agent (G) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, still more preferably 5 to 30% by mass, based on the total solid content of the resist composition.

As described above, the composition of the present invention may or may not contain a cross-linking agent, but preferably does not contain a cross-linking agent.

<Surfactant>

The composition of the present invention preferably contains a surfactant. When a surfactant is contained, a fluorine-based and / or a 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, a pattern having good sensitivity and resolution and few adhesions and development defects can be obtained when an exposure light source of 250 nm or less, particularly 220 nm or less is used. ..

Examples of the fluorine-based and / or silicon-based surfactant include the surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425.

In addition, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more.

When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, preferably 0.0005 to 1% by mass, based on the total solid content of the composition. More preferred.

On the other hand, when the content of the surfactant is 10 ppm (parts per million) or more with respect to the total solid content of the composition, the surface uneven distribution of the hydrophobic resin is increased. As a result, the surface of the sensitive light-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability during immersion exposure is improved.

<Resin (J)>

When the composition of the present invention contains a cross-linking agent (G), the composition of the present invention preferably contains an alkali-soluble resin (J) having a phenolic hydroxyl group (also referred to as "resin (J)"). The resin (J) preferably contains a repeating unit having a phenolic hydroxyl group.

In this case, typically a negative pattern is preferably formed.

The cross-linking agent (G) may be supported on the resin (J).

The resin (J) may contain the above-mentioned acid-degradable group.

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

In general formula (II),

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

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

Ar'represents an aromatic ring group.

m represents an integer of 1 or more.

The resin (J) may be used alone or in combination of two or more.

The content of the resin (J) in the total solid content of the composition of the present invention is generally 30% by mass or more. 40% by mass or more is preferable, and 50% by mass or more is more preferable. The upper limit is not particularly limited, but 99% by mass or less is preferable, 90% by mass or less is more preferable, and 85% by mass or less is further preferable.

As the resin (J), the resin 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.

These plasticizers may be used alone or in combination of two or more.

When the composition of the present invention contains a plasticizer, the content of the plasticizer is preferably 0.01 to 20% by mass, more preferably 1 to 15% by mass, based on the total solid content of the composition.

<Preparation method>

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

The film thickness of the actinic cheilitis or radiation-sensitive film (resist film) made of the composition of the present invention is preferably 1 μm or more, and for the purpose of increasing the number of processing steps, improving the imprint resistance, and the like. 3 μm or more is more preferable, 5 μm or more is further preferable, and 10 μm or more is particularly preferable. The upper limit is not particularly limited, but is, for example, 100 μm or less.

As will be described later, a pattern can be formed from the composition of the present invention.

The film thickness of the formed pattern is 1 μm or more, and is more preferably 3 μm or more, further preferably 5 μm or more, and particularly preferably 10 μm or more, for the purpose of increasing the number of processing steps and improving the impla resistance. The upper limit is not particularly limited, but is, for example, 100 μm or less.

In the composition of the present invention, the above-mentioned components are dissolved in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtered through a filter, and then applied onto a predetermined support (substrate) for use. The pore size of the filter used for filter filtration is preferably 0.2 μm or less, more preferably 0.05 μm or less, and even more 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 0.2 μm or less. More preferred. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Laid-Open No. 2002-62667), cyclic filtration may be performed, and a plurality of types of filters may be arranged in series or in parallel. It may be connected to and filtered. Moreover, the composition may be filtered a plurality of times. Further, the composition may be degassed before and after the filter filtration.

The composition of the present invention preferably has a viscosity of 100 to 700 mPa · s. The viscosity of the composition of the present invention is more preferably 100 to 500 mPa · s in that it is more excellent in coatability.

The viscosity can be measured with an E-type viscometer.

<Use>

The composition of the present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition whose properties change in response to irradiation with active light or radiation. More specifically, the composition of the present invention comprises a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board manufacturing such as a liquid crystal or a thermal head, a molding structure for imprinting, another photofabrication step, or a photofabrication step. It relates to a sensitive light-sensitive or radiation-sensitive resin composition used for producing a flat plate printing plate or an acid-curable composition. The pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, a MEMS (Micro Electro Mechanical Systems), and the like.

[Pattern formation method]

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

The pattern forming method of the present invention

(I) A step of forming a resist film (actinic cheilitis or radiation-sensitive film) on a support by the above-mentioned actinic cheilitis or radiation-sensitive resin composition (resist film forming step).

(Ii) A step (exposure step) of exposing the resist film (irradiating active light rays or radiation), and

(Iii) It has a step (development step) of developing the exposed resist film with a developing solution.

The pattern forming method of the present invention is not particularly limited as long as it includes the above steps (i) to (iii), and may further include the following steps.

In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be immersion exposure.

The pattern forming method of the present invention preferably includes (iv) preheating (PB: PreBake) step before the (ii) exposure step.

The pattern forming method of the present invention preferably includes (v) post-exposure heating (PEB: Post Exposure Bake) step after the (ii) exposure step and before the (iii) development step.

The pattern forming method of the present invention may include (ii) exposure steps a plurality of times.

The pattern forming method of the present invention may include (iv) a preheating step a plurality of times.

The pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.

In the pattern forming method of the present invention, the above-mentioned (i) resist film forming step, (ii) exposure step, and (iii) developing step can be performed by a generally known method.

In the pattern forming method of the present invention, (i) the film thickness of the sensitive light-sensitive or radiation-sensitive film formed on the substrate in the resist film forming step is preferably 1 μm or more and 3 μm as described above. The above is more preferable, 5 μm or more is further preferable, and 10 μm or more is particularly preferable. The upper limit is not particularly limited, but is, for example, 100 μm or less.

Further, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support. As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.

A protective film (top coat) may be formed on the upper layer of the resist film. As the protective film, a known material can be appropriately used. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/02444438 and International Patent Application Publication No. 2016/157988A can be preferably used. The composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent.

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 is generally used in a semiconductor manufacturing process such as an IC, a circuit board manufacturing process such as a liquid crystal display or a thermal head, and other photolithography lithography processes. A substrate can be used. Specific examples of the support include an _{inorganic substrate such as silicon, SiO 2} , and SiN.

The heating temperature is preferably 70 to 150 ° C., more preferably 70 to 130 ° C., further preferably 80 to 130 ° C., and even more preferably 80 to 120 ° C. in both the (iv) preheating step and the (v) post-exposure heating step. Is the most preferable.

The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, still more preferably 30 to 90 seconds in both the (iv) preheating step and the (v) post-exposure heating step.

The heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed by using a hot plate or the like.

The wavelength of the light source used in the exposure process is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, polar ultraviolet light (EUV), X-ray, and electron beam. Among these, 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), and an electron beam or the like, KrF excimer laser, ArF excimer laser , EUV or electron beam is preferable, and KrF excimer laser is more preferable.

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

As the alkaline developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but in addition to this, alkaline aqueous solutions such as inorganic alkali, 1st to 3rd amine, alcohol amine, and cyclic amine are also used. It can be used.

Further, the alkaline developer may contain an appropriate amount of alcohols 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 with 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 developer is a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. It is preferable to have it.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutyl ketone. Cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate and the like can be mentioned.

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

As the alcohol solvent, the amide solvent, the ether solvent, and the hydrocarbon 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 solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.

The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. % Is particularly preferable.

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

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

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

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

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

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

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

The rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a general solution containing an organic solvent can be used. As the rinsing solution, a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is used. Is preferable.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent include the same as those described for the developing solution containing the organic solvent.

As the rinsing solution used in the rinsing step in this case, a rinsing solution containing a monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1 -Heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methylisobutylcarbinol can be mentioned. 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, methylisobutylcarbinol and the like. ..

A plurality of each component may be mixed, or may be mixed and used with an organic solvent other than the above.

The water content in the rinse solution is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. Good development characteristics can be obtained by setting the water content to 10% by mass or less.

The rinse solution may contain an appropriate amount of a surfactant.

In the rinsing step, the substrate developed with an organic developer is washed with a rinsing solution containing an organic solvent. The cleaning treatment method is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method of spraying a rinse liquid on the substrate surface (spray method). Above all, it is preferable to perform the cleaning treatment by the rotary coating method, and after cleaning, rotate the substrate at a rotation speed of 2,000 to 4,000 rpm (revolution per minute) to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. This heating step removes the developer and rinse liquid remaining between the patterns and inside the pattern. 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, 30 seconds to 30 seconds. 90 seconds is preferable.

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

Examples of the method for removing impurities such as metals from the various materials include filtration using a filter. The filter pore size is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one that has been pre-cleaned with an organic solvent. Filter In the filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step. The filter preferably has a reduced amount of eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426).

In addition to filter filtration, impurities may be removed by an adsorbent, or filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent 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. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500).

Further, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. Alternatively, a method such as lining the inside of the apparatus with Teflon (registered trademark) or the like to perform distillation under conditions in which contamination is suppressed as much as possible can be mentioned. The preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.

The above-mentioned various materials are described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351), etc. in order to prevent contamination with impurities. It is preferable to store it in a container.

A method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. Examples of the method for improving the surface roughness of the pattern include a method of treating the pattern with a plasma of a hydrogen-containing gas disclosed in US Patent Application Publication No. 2015/010497. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. A known method as described in 8328 83280N-1 “EUV Resist Curing Technology for LWR Reduction and Etch Sensitivity Enhancement” may be applied.

Further, the pattern formed by the above method is a spacer process disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Application Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/209941. Can be used as a core material (Core).

[Manufacturing method of electronic devices]

The present invention also relates to a method for manufacturing an electronic device, including the above-mentioned pattern forming method. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric electronic device (for example, a home appliance, an OA (Office Automation) related device, a media related device, an optical device, a communication device, etc.). Will be done.

Hereinafter, the present invention will be described in more detail based on Examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

<Resin>

For the resin used, the structure of the repeating unit and its content (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) are shown.

The weight average molecular weight (Mw) and the dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). The content of the repeating unit ^{was measured by 13} C-NMR (nuclear magnetic resonance).

For each resin, the content (mol%) of the repeating unit (a1) derived from the monomer (monomer a1) having a glass transition temperature of 50 ° C. or less when made into a homopolymer, the type of the monomer a1, and the monomer a1 are homozygous. Corresponds to the glass transition temperature (Tg) when made into a polymer, the type of monomer corresponding to the repeating unit (a2) having an acid-degradable group, the content of the repeating unit (a2), and the repeating unit (a3) having a carboxy group. Type of monomer to be used, content of repeating unit (a3), type of monomer corresponding to repeating unit (a4) having a phenolic hydroxyl group, content of repeating unit (a4), type of monomer corresponding to other repeating unit , And the contents of other repeating units are listed in Table 1.

(Method of measuring the glass transition temperature of homopolymer)

The glass transition temperature of the homopolymer was measured by the differential scanning calorimetry (DSC) method, if there was a catalog value or a literature value, if there was one. The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg was 18,000, and the dispersity (Mw / Mn) was 1.7. As the DSC apparatus, a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Co., Ltd. was used, and the temperature rising rate was measured at 10 ° C./min.

The homopolymer used for the measurement of Tg was synthesized by the following procedure using the corresponding monomer. The homopolymer is synthesized by a general drop polymerization method.

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

The glass transition temperature when the monomer (ME-2) corresponding to the other repeating unit contained in the resin IR-1 is homopolymer is 100 ° C., and the other repeating unit contained in the resin IR-2 can be used. The glass transition temperature when the corresponding monomer (ME-1) was homopolymerized was 54 ° C.

<Additives>

The compounds used as additives are shown below.

II-12: Polyvinyl butyral resin Mobile B16H (manufactured by Kuraray Co., Ltd., weight average molecular weight 16000) Tg = 84 ° C.

II-13: Polyester resin Vylon200 (manufactured by Toyobo Co., Ltd., number average molecular weight 17,000) Tg = 67 ° C.

II-14: Polyvinyl methyl ether resin Lutonal M40 (BASF, weight average molecular weight 50,000) Tg = -49 ° C.

<Photoacid generator>

The structure of the photoacid generator used is shown below.

<Acid diffusion control agent>

The acid diffusion control agent used is shown below.

<Surfactant>

The surfactants used are shown below.

G-2: Troysol S366 (silicone surfactant manufactured by Troy Chemical Co., Ltd.)

G-3: Megafuck-R4 (fluorine-based surfactant manufactured by DIC Corporation)

<Solvent>

The solvent used is shown below.

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

S-2: Propylene glycol monomethyl ether (PGME)

S-3: Ethyl lactate (EL)

S-4: Butyl acetate (nBA)

S-5: Ethyl 3-ethoxypropionate (EEP)

S-6: Cyclohexanone

<Other additives>

The following compounds were used as other additives.

<Preparation of Actinic Cheilitis or Radiation Sensitive Resin Composition>

Each component shown in Table 2, Table 3 and Table 4 was mixed so as to have the solid content concentration (mass%) shown in Table 2, Table 3 and Table 4 to obtain a solution. Then, the obtained solution is filtered through a polyethylene filter having a pore size of 0.2 μm, whereby the actinic light-sensitive or radiation-sensitive resin composition (resist composition) res-1 to res-55, res-1X. ~ Res-4X was prepared. In the resist composition, the solid content means all components other than the solvent.

25 kinds (Na, K, Ca, Fe, Cu, Mg, Mn, Al, Li, Cr, Ni, Sn, Zn, Ag, As, Au, Ba, Cd, Co, Pb) contained in each composition. , Ti, V, W, Mo, Zr) were measured with an ICP-MS device (inductively coupled plasma mass spectrometer) "Agilent 7500cs" manufactured by Agilent Technologies, and the content of each metal species was Each was less than 10 ppb (parts-per-billion).

In Tables 2, 3 and 4, the content (% by mass) of each component other than the solvent means the content ratio to the total solid content. For the solvent, the amount (part by mass) of each used is described.

[Pattern formation and various evaluations]

<Pattern formation>

Using the spin coater "ACT-8" manufactured by Tokyo Electron, the prepared resist composition is applied onto a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane without providing an antireflection layer. Then, it was heated and dried at 130 ° C. for 60 seconds to form a positive resist film having the film thicknesses shown in Tables 5, 6 and 7. With respect to this resist film, using a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C wavelength 248 nm), NA (numerical aperture) = 0.6, σ = 0. Pattern exposure was performed under 75 exposure conditions. After irradiation, it was baked at 130 ° C. for 60 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried.

The dot pattern formed by exposure through a mask having an isolated dot pattern such that the dot pattern after reduced projection exposure is 3 μm × 3 μm and the pitch is 33 μm in both the vertical and horizontal directions is 3 μm square. ^{The optimum exposure amount (sensitivity) (mJ / cm 2} ) was defined as the exposure amount such that the pitch was 33 μm. A scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the dot pattern width.

By the above procedure, a pattern wafer having a substrate and a pattern (resist pattern) formed on the substrate surface was obtained.

<Evaluation of dot resolution>

Using the above-mentioned mask, the exposure amount was changed, and the dot pattern width of the obtained resist pattern was observed. The finest dot pattern width (μm) of the obtained resist pattern dot pattern width was used as an index for resolution evaluation, and was evaluated according to the following criteria.

A: 1 μm square dot pattern resolves

B: 1 μm square dot pattern does not resolve, but 3 μm square dot pattern resolves

C: 3 μm square dot pattern is not resolved, but 5 μm square dot pattern is resolved

D: Does not resolve even a 10 μm square dot pattern

<Evaluation of PCD performance>

Using the Tokyo Electron spin coater "ACT-8", the prepared resist composition is applied onto a hexamethyldisilazane-treated Si substrate (manufactured by Advanced Materials Technology) without providing an antireflection layer. Then, it was dried and baked to form a resist film on the substrate. Then, each substrate having a resist film was stored for a certain period of time in a clean room environment (this time is referred to as "storage time"). Then, the resist film after storage was pattern-exposed with the following optimum exposure amount through the following mask using a KrF excimer laser scanner. After irradiation, it was baked at 130 ° C. for 60 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried.

The dot pattern formed by exposure through a mask having an isolated dot pattern such that the dot pattern after reduced projection exposure is 3 μm × 3 μm and the pitch is 33 μm in both the vertical and horizontal directions is 3 μm square. ^{The optimum exposure amount (sensitivity) (mJ / cm 2} ) was defined as the exposure amount such that the pitch was 33 μm. A scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the dot pattern width.

The longest storage time in which the dot width of the obtained pattern was within the range of 3 μm ± 30 nm was defined as “PCD time” and evaluated according to the following criteria.

A: PCD time is 60 minutes or more

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

C: PCD time is 10 minutes or more and less than 30 minutes

D: PCD time is less than 10 minutes

<Evaluation of roughness (etching LER) of the side wall of the pattern during etching>

The pattern was formed by the same method as the dot pattern forming method described above, except that the exposure was performed through a mask having a line and space pattern such that the space width after the reduced projection exposure was 3 μm and the pitch width was 33 μm. ..

The exposure amount that forms an isolated space pattern with a space width of 3 μm and a pitch width of 33 μm was defined as the optimum exposure amount (sensitivity) (mJ / cm ² ).

A Si substrate (8-inch silicon wafer) was dry-etched using the isolated space pattern formed at the above sensitivity as a processing mask. First, etching was performed using a fluorine-based gas to process a Si substrate. Here, 1 inch corresponds to 25.4 mm. As the etching conditions, _{a gas in which Ar: C 4} F ₆ : O ₂ is mixed at a flow rate ratio of 25: 1: 2 is used, and the processing pressure is 4 Pa, the source power is 500 W, the wafer bias is 700 W, the antenna bias is 600 W, and the processing is performed. The condition of time 60 seconds was applied. Subsequently, etching using oxygen gas was performed to process a resist mask pattern. As the etching conditions, _{a gas in which CF 4} : O ₂ was mixed at a flow rate ratio of 1:24 was used, and conditions of a processing pressure of 0.5 Pa, a source power of 700 W, an antenna bias of 100 W, and a processing time of 60 seconds were applied. ..

After repeating the above dry etching process 10 times, the wafer was cut, the side wall roughness of the resist was observed with a scanning electron microscope (SEM), and the evaluation was performed using the following indexes. The dry etching apparatus used was U-621 manufactured by Hitachi High-Technologies Corporation.

A: Almost no roughness can be seen

B: Roughness can be seen a little

C: Roughness is large

D: Roughness is large, and holes with a diameter size exceeding 30 nm are opened in the pattern.

(Evaluation of development residue)

On an 8-inch Si substrate (Advanced Materials Technology) treated with hexamethyldisilazane using a spin coater "ACT-8" manufactured by Tokyo Electron Limited (hereinafter, also referred to as "substrate"). The resist composition prepared above was dropped while the substrate was stationary without providing the antireflection layer. After dropping, the substrate is rotated, and the rotation speed is maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, further at 500 rpm for 3 seconds, again at 100 rpm for 2 seconds, and then the film thickness setting rotation. It was increased to a number (1200 rpm) and maintained for 60 seconds. Then, heat drying (PB) was performed on a hot plate at 130 ° C. for 60 seconds to form a positive resist film having the film thickness shown in Table 5, Table 6 or Table 7 below. The resist film was baked (PEB) for 60 seconds at the temperatures shown in Table 5, Table 6 or Table 7 below without pattern exposure, and 2.38 mass% tetramethylammonium hydroxide (TMAH) was used. After immersing in an aqueous solution for 60 seconds, rinse with pure water for 30 seconds, dry, and heat (Post Bake) at the temperatures shown in Table 5, Table 6 or Table 7 below to evaluate the development residue. It was created. This wafer was observed with a defect inspection device COMPLUS (manufactured by AMAT), and the presence or absence of residual defects was confirmed using a defect review SEM RS5500 (manufactured by Hitachi High-Technologies Corporation), and the number was counted. It was evaluated using the following indicators according to the number of residual defects counted.

A: 0

B: 1-5

C: 6 to 20

D: Over 20

From the results of Tables 5, 6 and 7, the resist composition of the example is excellent in the resolution of the isolated pattern when the pattern is formed from the thick resist film, and the development residue after the development of the pattern is obtained. It can be seen that the reduction is possible, the PCD performance is excellent, and the roughness on the side wall of the resist pattern that may occur during etching can be suppressed.

Claims (16)

A light-sensitive or radiation-sensitive resin composition containing a resin (A), a compound (B) having a glass transition temperature of 100 ° C. or lower, and a solvent.

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

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

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

The content of the compound (B) is 1% by mass or more with respect to the total solid content of the actinic cheilitis or radiation-sensitive resin composition.

A light-sensitive or radiation-sensitive resin composition having a solid content concentration of 10% by mass or more.

The sensitive light-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a1) is a repeating unit derived from a monomer having a glass transition temperature of 30 ° C. or lower when it is homopolymerized.

The actinic cheilitis or radiosensitivity according to claim 1 or 2, wherein the repeating unit (a1) has a non-acidolytic alkyl group having 2 or more carbon atoms, which may contain a heteroatom in the chain. Resin composition.

The actinic or radiation-sensitive resin composition according to claim 3, wherein the repeating unit (a1) is a repeating unit represented by the following general formula (1-2).

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

The actinic or radiation-sensitive resin composition according to claim 1 or 2, wherein the repeating unit (a1) is a repeating unit represented by the following general formula (1-3).

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

The actinic or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the resin (A) contains a repeating unit (a4) having a phenolic hydroxyl group.

The actinic cheilitis or radiation-sensitive property according to any one of claims 1 to 6, wherein the content of the repeating unit (a2) is 50 mol% or less with respect to all the repeating units of the resin (A). Resin composition.

The actinic cheilitis according to any one of claims 1 to 7, wherein the content of the repeating unit (a2) is more than 19 mol% and 50 mol% or less with respect to all the repeating units of the resin (A). Or a radiation-sensitive resin composition.

The sensitivity according to any one of claims 1 to 8, wherein the content of the compound (B) is 20% by mass or less with respect to the total solid content of the actinic cheilitis or radiation-sensitive resin composition. A light or radiation sensitive resin composition.

The feeling according to any one of claims 1 to 9, wherein the content of the compound (B) is 5 to 15% by mass with respect to the total solid content of the actinic cheilitis or radiation-sensitive resin composition. Active light or radiation sensitive resin composition.

The actinic or radiation-sensitive resin composition according to any one of claims 1 to 10, wherein the compound (B) is a resin.

The actinic or radiation-sensitive resin composition according to any one of claims 1 to 10, wherein the compound (B) is a compound having a molecular weight of 100 to 5000.

The actinic or radiation-sensitive resin composition according to claim 11 or 12, wherein the compound (B) is a non-ether compound.

A resist film formed of the actinic or radiation-sensitive resin composition according to any one of claims 1 to 13.

(I) A step of forming a sensitive light-sensitive or radiation-sensitive film on a substrate with a sensitive light-sensitive or radiation-sensitive resin composition.

(Ii) A step of irradiating the sensitive light or radiation sensitive film with active light or radiation.

as well as,

(Iii) A pattern forming method comprising a step of developing a sensitive light-sensitive or radiation-sensitive film irradiated with the active light beam or radiation using a developing solution.

The pattern forming method, wherein the sensitive light-sensitive or radiation-sensitive resin composition is the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 13.

A method for manufacturing an electronic device, which comprises the pattern forming method according to claim 15.