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

Abstract

The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition, an etching resist film formed by the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. The actinic ray-sensitive or radiation-sensitive resin composition contains: a resin comprising non-acid-degradable repeating units derived from a monomer having a glass transition temperature of 50°C or less when set as a homopolymer and repeating units having an acid-degradable group; and a compound represented by the general formula (P‑1). Ring Q1 is a 4- to 6-membered ring. Among them, ring Q1 can form a condensed ring with other rings. As a ring element, ring Q1 has at least 2 carbon atoms, and S + The atoms of the ring elements directly bonded are carbon atoms. P1 ~R P5 R each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. P1 ~R P5 At least two of Z may be bonded to form a ring. ‑ Represents a non-nucleophilic anion.

Description

Technical Field

[0001] The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method and a method for producing an electronic device. Background Art

[0002] In order to compensate for the sensitivity drop caused by light absorption after the KrF excimer laser (248nm) resist is used, a chemical amplification image forming method is used as the resist image forming method. For example, as a positive chemical amplification image forming method, the following image forming method can be cited: by exposing the photoacid generator of the exposed part by excimer laser, electron beam, extreme ultraviolet light, etc., decomposing the photoacid generator to generate acid, using the generated acid as a reaction catalyst by baking (PEB: Post Exposure Bake) after the exposure to change the alkali-insoluble group into an alkali-soluble group, and removing the exposed part by an alkaline developer.

[0003] On the other hand, the miniaturization of the wavelength of the exposure light source has recently reached its limit, and the three-dimensionalization of the memory layer for the purpose of increasing capacity has become the mainstream, especially in the implantation process and NAND memory (NOT AND memory). The three-dimensionalization of the memory layer requires an increase in the number of processing stages along the vertical direction, so the resist film is required to be thickened from the previous nanometer size to the micrometer size.

[0004] For example, Patent Documents 1 and 2 describe thick-film chemically amplified positive photoresist compositions for forming thick-film photoresist layers.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2007-206425

[0008] Patent Document 2: Japanese Patent Application Publication No. 2008-191218 Summary of the invention

[0009] Technical issues to be solved by the invention

[0010] However, when etching of the object to be etched is performed using a pattern of a thick film formed by photolithography as a mask in the resist composition described in Patent Documents 1 or 2, pores (voids) are found to be dispersed inside the pattern. As pores, there are two types of pores, pores with a size of 50 nm or more (also referred to as "macropores") and pores with a size of less than 50 nm (also referred to as "small pores").

[0011] The present invention aims to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern in which macrovoids and microvoids are less likely to be generated inside the pattern during etching, a resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0012] Means for solving technical problems

[0013] The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that an actinic ray-sensitive or radiation-sensitive resin composition containing a specific resin and a compound of a specific structure that generates an acid upon irradiation with actinic rays or radiation (photoacid generator of a specific structure) can solve the above problems, thereby completing the present invention.

[0014] That is, the present inventors have found that the above-mentioned object can be achieved by the following structure.

[0015] <1> An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A) and a compound that generates an acid upon irradiation with actinic rays or radiation, wherein the actinic ray-sensitive or radiation-sensitive resin composition

[0016] The resin (A) comprises a repeating unit (a1) derived from a monomer having a glass transition temperature of 50° C. or less when formed as a homopolymer and a repeating unit (a2) having an acid-decomposable group.

[0017] The above-mentioned repeating unit (a1) is a non-acid-decomposable repeating unit.

[0018] The compound that generates an acid upon irradiation with the above-mentioned actinic rays or radiation includes a compound represented by the following general formula (P-1).

[0019] [Chemical formula 1]

[0020]

[0021] In the above general formula (P-1),

[0022] Q1 means including S + Ring.

[0023] Ring Q1 is a 4-membered ring, a 5-membered ring or a 6-membered ring, wherein Ring Q1 may form a condensed ring with other rings.

[0024] As ring elements, ring Q1 has at least 2 carbon atoms, + The atoms to which the ring elements are directly bonded are carbon atoms.

[0025] R P1 ~R P5R each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. P1 ~R P5 At least two of them may be bonded to form a ring.

[0026] Z - Represents a non-nucleophilic anion.

[0027] <2> The actinic ray-sensitive or radiation-sensitive resin composition according to <1>, wherein

[0028] The above-mentioned Q1 is a non-aromatic ring.

[0029] <3> The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <2>, wherein

[0030] As ring elements, the above Q1 has S + Other heteroatoms.

[0031] <4> The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <2>,

[0032] in,

[0033] The compound represented by the above general formula (P-1) is a compound represented by the following general formula (P-2).

[0034] [Chemical formula 2]

[0035]

[0036] In the above general formula (P-2),

[0037] R P1 ~R P5 R each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. P1 ~R P5 At least two of them may be bonded to form a ring.

[0038] R P6 ~R P9 Each independently represents a hydrogen atom or a substituent.

[0039] m1 and m2 each independently represent 1 or 2.

[0040] R P6 ~R P9 When there are plural of each, they may be the same or different.

[0041] When m1 represents 2, 2 R P6 They may be bonded to each other to form a ring.

[0042] When m2 represents 2, 2 R P8 They may be bonded to each other to form a ring.

[0043] M1 represents a heteroatom or -CR P10 R P11 -. R P10 and R P11 Each independently represents a hydrogen atom or a substituent.

[0044] Z - Represents a non-nucleophilic anion.

[0045] <5> The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <2>,

[0046] in,

[0047] The compound represented by the above general formula (P-1) is a compound represented by the following general formula (P-3).

[0048] [Chemical formula 3]

[0049]

[0050] In the above general formula (P-3),

[0051] R P1 , R P2 , R P4 and R P5 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group.

[0052] R P6 ~R P9 Each independently represents a hydrogen atom or a substituent.

[0053] m1 and m2 each independently represent 1 or 2.

[0054] R P6 ~R P9 When there are plural of each, they may be the same or different.

[0055] When m1 represents 2, 2 R P6 They may be bonded to each other to form a ring.

[0056] When m2 represents 2, 2 R P8 They may be bonded to each other to form a ring.

[0057] M1 represents a heteroatom or -CR P10 R P11 -. R P10 and R P11 Each independently represents a hydrogen atom or a substituent.

[0058] R P12 represents a hydrogen atom or an alkyl group.

[0059] R P1 , R P2 , R P4 , R P5 and R P12 At least two of them may be bonded to form a ring.

[0060] Z - Represents a non-nucleophilic anion.

[0061] <6> The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <5>, wherein

[0062] The compound represented by the above general formula (P-1) is a compound represented by the following general formula (P-4) or (P-5).

[0063] [Chemical formula 4]

[0064]

[0065] [Chemical formula 5]

[0066]

[0067] In the above general formulas (P-4) and (P-5),

[0068] R P1 , R P2 , R P4 and R P5 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group.

[0069] R P6 ~R P9 Each independently represents a hydrogen atom or a substituent.

[0070] There are multiple R P6 ~R P9 They can be the same or different.

[0071] 2 Rs P6 They may be bonded to each other to form a ring.

[0072] 2 R's P8 They may be bonded to each other to form a ring.

[0073] M1 represents a heteroatom or -CR P10 R P11 -. R P10 and R P11 Each independently represents a hydrogen atom or a substituent.

[0074] R P12 represents a hydrogen atom or an alkyl group.

[0075] R P1 , R P2 , R P4 , R P5 and R P12 At least two of them may be bonded to form a ring.

[0076] Z - Represents a non-nucleophilic anion.

[0077] In the above general formula (P-5), R P13 represents a hydrogen atom or a substituent.

[0078] <7> The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <6>, wherein

[0079] The solid content concentration is 10% by mass or more.

[0080] <8> The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <7>, wherein

[0081] The above Z - It is an anion represented by any one of the following general formulae (Z1) to (Z4).

[0082] [Chemical formula 6]

[0083]

[0084] In the general formula (Z1), R Z1 It represents an alkyl group.

[0085] [Chemical formula 7]

[0086]

[0087] In the general formula (Z2),

[0088] Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. A plurality of Xf may be the same or different.

[0089] R Z2 and R Z3 Each independently represents a hydrogen atom, a fluorine atom or an alkyl group. Z2 and R Z3 They can be the same or different.

[0090] L Z1 represents a divalent linking group, and when there are multiple LZ1 It can be the same or different.

[0091] A Z1 It represents an organic group containing a ring structure.

[0092] x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

[0093] [Chemical formula 8]

[0094]

[0095] In general formulae (Z3) and (Z4), Rb3 to Rb7 each independently represent an alkyl group, a cycloalkyl group or an aryl group. Rb3 and Rb4 may be bonded to form a ring structure. Rb5 and Rb6 may be bonded to form a ring structure.

[0096] <9> The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <8>, wherein

[0097] The resin (A) contains a repeating unit having an aromatic ring.

[0098] <10> A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <9>.

[0099] <11> A pattern forming method, comprising:

[0100] (i) forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 1 μm or more on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition;

[0101] (ii) irradiating the actinic ray or radiation sensitive film with actinic rays or radiation having a wavelength of 200 to 300 nm; and

[0102] (iii) a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation using a developer,

[0103] The above-mentioned actinic ray-sensitive or radiation-sensitive resin composition contains a resin (A) and a compound that generates an acid upon irradiation with actinic rays or radiation.

[0104] The resin (A) comprises a repeating unit (a1) derived from a monomer having a glass transition temperature of 50° C. or less when formed as a homopolymer and a repeating unit (a2) having an acid-decomposable group.

[0105] The above-mentioned repeating unit (a1) is a non-acid-decomposable repeating unit.

[0106] The compound that generates an acid upon irradiation with the above-mentioned actinic rays or radiation includes a compound represented by the following general formula (P-1).

[0107] [Chemical formula 9]

[0108]

[0109] In the above general formula (P-1),

[0110] Q1 means including S + Ring.

[0111] Ring Q1 is a 4-membered ring, a 5-membered ring or a 6-membered ring, wherein Ring Q1 may form a condensed ring with other rings.

[0112] As ring elements, ring Q1 has at least 2 carbon atoms, + The atoms to which the ring elements are directly bonded are carbon atoms.

[0113] R P1 ~R P5 R each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. P1 ~R P5 At least two of them may be bonded to form a ring.

[0114] Z - Represents a non-nucleophilic anion.

[0115] <12> A method for manufacturing an electronic device, comprising the pattern forming method described in <11>.

[0116] Effects of the Invention

[0117] According to the present invention, there can be provided an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern in which macrovoids and microvoids are less likely to be generated inside the pattern during etching, a resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. DETAILED DESCRIPTION

[0118] Hereinafter, the present invention will be described in detail.

[0119] Although the description of the constituent elements described below may be made based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

[0120] "Actinic rays" or "radiation" in this specification refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB). "Light" in this specification refers to actinic rays or radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV), and X-rays, but also drawing using particle beams such as electron beams and ion beams.

[0121] In this specification, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0122] In the present specification, (meth)acrylate refers to at least one of acrylate and methacrylate, and (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0123] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (also called molecular weight distribution) (Mw / Mn) of the resin are defined as polystyrene conversion values ​​based on GPC (Gel Permeation Chromatography) measurement by a GPC (HLC-8120GPC manufactured by TOSOH CORPORATION) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0124] In the group (atomic group) marking in this specification, the marking without substitution and unsubstituted includes groups without substitution and groups with substitution. For example, "alkyl" means not only alkyl without substitution (unsubstituted alkyl) but also alkyl with substitution (substituted alkyl). In addition, "organic group" in this specification refers to a group containing at least one carbon atom.

[0125] Furthermore, in the present specification, when “may have a substituent”, the type of the substituent, the position of the substituent, and the number of the substituent are not particularly limited. The number of substituents may be, for example, 1, 2, 3, or more. As examples of substituents, monovalent non-metallic atomic groups other than hydrogen atoms may be cited, for example, substituents T below may be selected.

[0126] (Substituent T)

[0127] Examples of the substituent T include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; alkoxy groups such as methoxy, ethoxy and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl and methacryloyl; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamido groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups; and combinations thereof.

[0128] [Acticular ray-sensitive or radiation-sensitive resin composition]

[0129] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also simply referred to as "the composition of the present invention") contains a resin (A) and a compound that generates an acid by irradiation with actinic rays or radiation, wherein the resin (A) contains a repeating unit (a1) derived from a monomer having a glass transition temperature of 50°C or less when set as a homopolymer and a repeating unit (a2) having an acid-decomposable group, wherein the repeating unit (a1) is a non-acid-decomposable repeating unit, and the compound that generates an acid by irradiation with the actinic ray or radiation contains a compound represented by the following general formula (P-1).

[0130] [Chemical formula 10]

[0131]

[0132] In the above general formula (P-1),

[0133] Q1 means including S + Ring.

[0134] Ring Q1 is a 4-membered ring, a 5-membered ring or a 6-membered ring, wherein Ring Q1 may form a condensed ring with other rings.

[0135] As ring elements, ring Q1 has at least 2 carbon atoms, + The atoms to which the ring elements are directly bonded are carbon atoms.

[0136] R P1 ~R P5 R each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. P1 ~R P5 At least two of them may be bonded to form a ring.

[0137] Z - Represents a non-nucleophilic anion.

[0138] The composition of the present invention is a so-called resist composition, which can be a positive resist composition or a negative resist composition. Furthermore, it can be a resist composition for alkali development or a resist composition for organic solvent development. Among them, a positive resist composition and a resist composition for alkaline development are preferred.

[0139] The composition of the present invention is typically a chemically amplified resist composition.

[0140] The composition of the present invention may or may not contain a crosslinking agent (a compound that crosslinks the resin (A) by the action of an acid), but preferably does not contain a crosslinking agent.

[0141] The reason why the composition of the present invention can form a pattern in which large voids and small voids are less likely to be generated inside the pattern during etching is not clear in detail, but is presumed as follows.

[0142] When a resist film is formed using a resist composition containing an acid-decomposable resin and a photoacid generator, the photoacid generator usually remains in the pattern (resist pattern) obtained by exposure and alkali development. In addition, during the vacuuming process performed when etching (typically plasma etching) the object to be etched using the pattern as a mask, macropores and micropores are generated due to the decomposition products of the photoacid generator remaining in the pattern.

[0143] The present inventors have found that the plasticity of the pattern can be improved by using a resin (resin (A)) having a repeating unit (repeating unit (a1)) derived from a monomer having a glass transition temperature of 50° C. or less when used as a homopolymer as an acid-decomposable resin. This makes it possible to easily remove the decomposition products of the photoacid generator from the inside of the pattern by volatilization, and reduce macrovoids.

[0144] However, even when the resin (A) is used, there is still room for improvement in reducing the microvoids.

[0145] Therefore, the inventors conducted in-depth research and found that if the cation of the photoacid generator decomposed by exposure is highly volatile, it will volatilize before etching, so it will not remain inside the pattern, and the generation of pores during etching can be suppressed. In addition, it was found that by using the resin (A) and the photoacid generator represented by the general formula (P-1) at the same time, not only large pores but also small pores can be greatly reduced. In particular, it was found that according to the present invention, extremely small pores with a size of less than 20 nm can also be reduced.

[0146] Furthermore, in the acid-decomposable resin (resin (A)) of the present invention, the repeating unit (a1) is a non-acid-decomposable repeating unit. This is because the effect of the present invention cannot be exerted when the repeating unit derived from a monomer having a glass transition temperature of 50°C or less when set as a homopolymer is an acid-decomposable repeating unit (for example, a repeating unit derived from tert-butyl acrylate). That is, under the environment during etching, the photoacid generator remaining inside the pattern decomposes to generate acid, and a deprotection reaction of the remaining acid-decomposable repeating unit is performed. For example, the repeating unit derived from tert-butyl acrylate becomes a repeating unit derived from acrylic acid through a deprotection reaction. Here, it is considered that acrylic acid is derived from a monomer having a glass transition temperature higher than 50°C when set as a homopolymer, so it becomes impossible to improve the plasticity of the pattern and the pore reduction effect cannot be obtained.

[0147] <Resin (A)>

[0148] The resin (A) contained in the composition of the present invention comprises a repeating unit (a1) derived from a monomer having a glass transition temperature (Tg) of 50° C. or less when formed into a homopolymer, and a repeating unit (a2) having an acid-decomposable group, wherein the repeating unit (a1) is a non-acid-decomposable repeating unit.

[0149] Since the resin (A) contains a repeating unit having an acid-decomposable group, it is a resin (acid-decomposable resin) that is decomposed by the action of an acid to increase its polarity. That is, in the pattern forming method of the present invention described later, when an alkaline developer is typically used as a developer, a positive pattern can be preferably formed, and when an organic developer is used as a developer, a negative pattern can be preferably formed.

[0150] (Repeating unit (a1))

[0151] The repeating unit (a1) is a repeating unit derived from a monomer having a glass transition temperature of 50° C. or less when formed as a homopolymer (also referred to as “monomer a1”).

[0152] Furthermore, the repeating unit (a1) is a non-acid decomposable repeating unit.

[0153] It does not have an acid-decomposable group.

[0154] (Method for measuring glass transition temperature of homopolymer)

[0155] When there is a catalog value or literature value, the glass transition temperature of the homopolymer is adopted. If there is no value, it is measured by differential scanning calorimetry (DSC). The weight average molecular weight (Mw) of the homopolymer used for Tg measurement is set to 18,000, and the dispersion (Mw / Mn) is set to 1.7. A thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Inc. is used as the DSC device, and the measurement is performed at a heating rate of 10°C / min.

[0156] The homopolymer used for measuring Tg may be synthesized by a known method using a corresponding monomer, and can be synthesized, for example, by a general dropping polymerization method, etc. An example is shown below.

[0157] 54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were heated to 80°C under a nitrogen flow. While stirring the 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 the addition was completed, it was further stirred at 80°C for 2 hours. After the reaction solution was cooled, it was reprecipitated with a large amount of methanol / water (mass ratio 9:1), filtered, and the obtained solid was dried to obtain a homopolymer (Mw: 18000, Mw / Mn: 1.7). The obtained homopolymer was used for DSC measurement. The DSC apparatus and heating rate are as described above.

[0158] There is no particular limitation on the monomer a1 as long as the glass transition temperature (Tg) when used as a homopolymer is 50°C or less, but from the viewpoint of reducing the voids inside the pattern, the Tg when used as a homopolymer is preferably 30°C or less. There is no particular limitation on the lower limit of the Tg when the monomer a1 is used as a homopolymer, but it is preferably -80°C or more, more preferably -70°C or more, further preferably -60°C or more, and particularly preferably -50°C or more.

[0159] As the repeating unit (a1), from the viewpoint of being able to easily volatilize the low molecular weight compound remaining in the film to the outside of the system, a repeating unit having a non-acid decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain is preferred. In the present specification, "non-acid decomposable" means having a property of not causing a separation / decomposition reaction by an acid generated by a photoacid generator.

[0160] More specifically, the “non-acid-decomposable alkyl group” includes an alkyl group that is not detached from the resin (A) by the action of the acid generated by the photoacid generator or an alkyl group that is not decomposed by the action of the acid generated by the photoacid generator.

[0161] The non-acid-decomposable alkyl group may be either linear or branched.

[0162] Hereinafter, the repeating unit having a non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain will be described.

[0163] The non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain is not particularly limited, and examples thereof include alkyl groups having 2 to 20 carbon atoms and alkyl groups having 2 to 20 carbon atoms which contain a heteroatom in the chain.

[0164] Examples of the alkyl group having 2 to 20 carbon atoms which may contain a heteroatom in the chain include alkyl groups in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group obtained by combining two or more of these groups. The above R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0165] Specific examples of the non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, octadecyl, isobutyl, sec-butyl, 1-ethylpentyl and 2-ethylhexyl, and monovalent alkyl groups in which one or more -CH2- of these groups are substituted with -O- or -O-CO-.

[0166] The number of carbon atoms in the non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain is preferably 2 or more and 16 or less, more preferably 2 or more and 10 or less, and even more preferably 2 or more and 8 or less.

[0167] Furthermore, the non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (eg, substituent T).

[0168] The repeating unit (a1) is preferably a repeating unit represented by the following general formula (1-2).

[0169] [Chemical formula 11]

[0170]

[0171] In the general formula (1-2), R1 represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group, and R2 represents a non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain.

[0172] The halogen atom represented by R1 is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0173] The alkyl group represented by R1 is not particularly limited, and examples thereof include alkyl groups having 1 to 10 carbon atoms, and specific examples thereof include methyl, ethyl, and tert-butyl groups, among which alkyl groups having 1 to 3 carbon atoms are preferred, and methyl groups are more preferred.

[0174] The cycloalkyl group represented by R1 is not particularly limited, and examples thereof include cycloalkyl groups having 5 to 10 carbon atoms, and more specifically, cyclohexyl groups and the like.

[0175] Among them, R1 is preferably a hydrogen atom or a methyl group.

[0176] The definition and preferred embodiments of the non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain represented by R2 are as described above.

[0177] Furthermore, from the viewpoint of being able to volatilize the low molecular weight compounds remaining in the film to the outside of the system, the repeating unit (a1) may be a repeating unit having a non-acid-decomposable alkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the ring element.

[0178] Hereinafter, a repeating unit having a non-acid-decomposable alkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in a ring element will be described.

[0179] The non-acid-decomposable alkyl group may be either linear or branched.

[0180] The number of carbon atoms of the non-acid-decomposable alkyl group is preferably 2 or more. From the viewpoint that the Tg of the homopolymer is 50° C. or less, the upper limit of the number of carbon atoms of the non-acid-decomposable alkyl group is preferably, for example, 20 or less.

[0181] The non-acid-decomposable alkyl group which may contain a heteroatom in the chain is not particularly limited, and examples thereof include alkyl groups having 2 to 20 carbon atoms and alkyl groups having 2 to 20 carbon atoms containing a heteroatom in the chain. In addition, at least one of the hydrogen atoms in the alkyl group is substituted with a carboxyl group or a hydroxyl group.

[0182] Examples of the alkyl group having 2 to 20 carbon atoms which may contain a heteroatom in the chain include alkyl groups in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group obtained by combining two or more of these groups. The above R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0183] The number of carbon atoms of the non-acid-decomposable alkyl group which may contain a heteroatom in the chain is preferably 2 to 16, more preferably 2 to 10, and even more preferably 2 to 8 from the viewpoint of suppressing voids in the pattern.

[0184] Furthermore, the non-acid-decomposable alkyl group may have a substituent (eg, substituent T).

[0185] Specific examples of the repeating unit having a non-acid-decomposable alkyl group having a carboxyl group and containing a heteroatom in the chain include repeating units having the following structures.

[0186] [Chemical formula 12]

[0187]

[0188] The number of carbon atoms of the non-acid-decomposable cycloalkyl group is preferably 5 or more. From the viewpoint of setting the Tg of the homopolymer to 50° C. or less, the upper limit of the number of carbon atoms of the non-acid-decomposable cycloalkyl group is, for example, preferably 20 or less, more preferably 16 or less, and even more preferably 10 or less.

[0189] The non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring element is not particularly limited, and examples thereof include a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group) and a cycloalkyl group having 5 to 20 carbon atoms containing a heteroatom in the ring element. In addition, at least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxyl group or a hydroxyl group.

[0190] Examples of cycloalkyl groups having 5 to 20 carbon atoms and containing a heteroatom in the ring element include cycloalkyl groups in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group obtained by combining two or more of these groups. The above R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0191] Furthermore, the non-acid-decomposable cycloalkyl group may have a substituent (eg, substituent T).

[0192] Among them, from the viewpoint of more excellent effects of the present invention, the repeating unit having a non-acid-decomposable alkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the ring element, is preferably a repeating unit represented by the following general formula (1-3).

[0193] [Chemical formula 13]

[0194]

[0195] In the general formula (1-3), R3 represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. R4 represents a non-acid decomposable alkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the chain, or a non-acid decomposable cycloalkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the ring element.

[0196] In the general formula (1-3), R3 has the same meaning as R1 above, and the preferred embodiments are also the same.

[0197] The definition and preferred embodiment of the non-acid-decomposable alkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the chain, or the non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in a ring element represented by R4 are as described above.

[0198] Among them, as R4, a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group which may contain a hetero atom as a ring element is preferred.

[0199] Examples of the monomer a1 include ethyl acrylate (-22°C), n-propyl acrylate (-37°C), isopropyl acrylate (-5°C), n-butyl acrylate (-55°C), n-butyl methacrylate (20°C), n-hexyl acrylate (-57°C), n-hexyl methacrylate (-5°C), n-octyl methacrylate (-20°C), 2-ethylhexyl acrylate (-70°C), isononyl acrylate (-82°C), lauryl methacrylate (-65°C), 2-hydroxyethyl acrylate (-15°C), 2-hydroxypropyl methacrylate (26°C), 1-[2-(methacryloyloxy)ethyl succinate] (9°C), 2-ethylhexyl methacrylate (-10°C), sec-butyl acrylate (-26°C), methoxypolyethylene glycol monomethacrylate (n=2) (-20°C), and hexadecyl acrylate (35°C). In addition, the term in parentheses indicates Tg (°C) as a homopolymer.

[0200] Methoxypolyethylene glycol monomethacrylate (n=2) is a compound having the following structure.

[0201] [Chemical formula 14]

[0202]

[0203] The resin (A) may contain only one type of repeating unit (a1), or may contain two or more types.

[0204] In the resin (A), the content of the repeating unit (a1) (the total of the repeating units (a1) when there are multiple repeating units) is preferably 5 mol% or more, more preferably 10 mol% or more, preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 30 mol% or less relative to all the repeating units of the resin (A). Among them, the content of the repeating unit (a1) in the resin (A) (the total of the repeating units (a1) when there are multiple repeating units) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, and further preferably 5 to 30 mol%.

[0205] (Repeating unit (a2))

[0206] The resin (A) contains a repeating unit (a2) having an acid-decomposable group.

[0207] The resin (A) may contain one type of repeating unit (a2) having an acid-decomposable group alone, or may contain two or more types simultaneously.

[0208] In the resin (A), the content of the repeating unit (a2) (the total of the repeating units (a2) when there are multiple repeating units) is preferably 20 mol% or less relative to all the repeating units of the resin (A), and is more preferably 15 mol% or less from the viewpoint of suppressing the voids inside the pattern and excellent etching resistance. In addition, the lower limit of the content of the repeating unit (a2) is, for example, 3 mol% or more, preferably 5 mol% or more relative to all the repeating units of the resin (A).

[0209] The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that is decomposed and released by the action of an acid.

[0210] Examples of the polar group include acidic groups (groups that dissociate in a 2.38% by mass tetramethylammonium hydroxide aqueous solution) such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic group, a sulfonylamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tri(alkylcarbonyl)methylene group, and a tri(alkylsulfonyl)methylene group, as well as an alcoholic hydroxyl group.

[0211] In addition, the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and as a hydroxyl group, an aliphatic alcohol (for example, a hexafluoroisopropanol group, etc.) substituted with an electron-withdrawing group such as a fluorine atom at the α position is excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less is preferred.

[0212] Preferred polar groups include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

[0213] Preferred acid-decomposable groups are groups in which the hydrogen atoms of these groups are substituted with groups that are detached by the action of an acid (leaving group).

[0214] Examples of the group that is released by the action of an acid (release group) include -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR39 ) and -C(R 01 )(R 02 )(OR 39 )wait.

[0215] In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0216] R 01 and R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0217] R 36 ~R 39 , R 01 and R 02 The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, and octyl groups.

[0218] R 36 ~R 39 , R 01 and R 02 The cycloalkyl group may be a monocyclic ring or a polycyclic ring.

[0219] As monocyclic cycloalkyl, cycloalkyl having 3 to 8 carbon atoms is preferred, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl can be mentioned. As polycyclic cycloalkyl, cycloalkyl having 6 to 20 carbon atoms is preferred, for example, adamantyl, norbornyl, isobornyl, bornyl, dicyclopentyl, α-pinenyl, tricyclodecyl, tetracyclododecyl and androstanyl can be mentioned. In addition, at least one carbon atom in the cycloalkyl may be substituted by a heteroatom such as an oxygen atom.

[0220] R 36 ~R 39 , R 01 and R 02 The aryl group is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl.

[0221] R 36 ~R 39 , R 01 and R 02 The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, and naphthylmethyl.

[0222] R 36 ~R 39 , R 01 and R02 The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, butenyl and cyclohexenyl.

[0223] As R 36 With R 37 The ring formed by mutually bonding is preferably a cycloalkyl group (monocyclic or polycyclic). As the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl groups are preferred.

[0224] As the acid-decomposable group, a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, or the like is preferred, and an acetal ester group or a tertiary alkyl ester group is more preferred.

[0225] Repeating units having a structure in which a -COO- group is protected by a leaving group that is decomposed and released by the action of an acid (acid-decomposable group)

[0226] As the repeating unit having an acid-decomposable group, the resin (A) preferably has a repeating unit represented by the following general formula (AI).

[0227] [Chemical formula 15]

[0228]

[0229] In the general formula (AI),

[0230] Xa1 represents a hydrogen atom, a halogen atom or a monovalent organic group.

[0231] T represents a single bond or a divalent linking group.

[0232] Rx1 to Rx3 each independently represent an alkyl group or a cycloalkyl group.

[0233] Any two of Rx1 to Rx3 may be bonded to form a ring structure, or may not form a ring structure.

[0234] Examples of the divalent linking group for 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.

[0235] T is preferably a single bond or a -COO-Rt- group. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and more preferably -CH2-, -(CH2)2- or -(CH2)3-. T is more preferably a single bond.

[0236] Xa1 is preferably a hydrogen atom or an alkyl group.

[0237] The alkyl group of Xa1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

[0238] The alkyl group of Xa1 preferably has 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, hydroxymethyl, and trifluoromethyl. The alkyl group of Xa1 is preferably methyl.

[0239] The alkyl group of Rx1, Rx2 and Rx3 may be linear or branched, and is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. In the alkyl group of Rx1, Rx2 and Rx3, a part of the carbon-carbon bond may be a double bond.

[0240] The cycloalkyl group for Rx1, Rx2 and Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0241] As the ring structure formed by 2 bonds in Rx1, Rx2 and Rx3, the cycloalkane ring of monocyclic rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring and cyclooctane ring or the cycloalkyl rings of polycyclic rings such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring and adamantane ring are preferred. Among them, cyclopentyl ring, cyclohexyl ring or adamantane ring are more preferred. As the ring structure formed by 2 bonds in Rx1, Rx2 and Rx3, the structure shown below is also preferred.

[0242] [Chemical formula 16]

[0243]

[0244] Specific examples of monomers corresponding to the repeating unit represented by the general formula (AI) are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to the case where Xa1 in the general formula (AI) is a methyl group, but Xa1 can be arbitrarily substituted with a hydrogen atom, a halogen atom or a monovalent organic group.

[0245] [Chemical formula 17]

[0246]

[0247] It is also preferred that the resin (A) has a repeating unit described in paragraphs <0336> to <0369> of the specification of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having an acid-decomposable group.

[0248] Furthermore, the resin (A) may have, as a repeating unit having an acid-decomposable group, a repeating unit containing a group that is decomposed by an acid to generate an alcoholic hydroxyl group as described in paragraphs <0363> to <0364> of US Patent Application Publication No. 2016 / 0070167A1.

[0249] Repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of an acid (acid-decomposable group)

[0250] As the repeating unit having an acid-decomposable group, it is preferred that the resin (A) contains a repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of an acid. In addition, in this specification, a phenolic hydroxyl group is a group formed by replacing 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.

[0251] Examples of the leaving group that is decomposed and released by the action of an acid include groups represented by formulae (Y1) to (Y4).

[0252] Formula (Y1): -C(Rx1)(Rx2)(Rx3)

[0253] Formula (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0254] Formula (Y3): -C(R 36 )(R 37 )(OR 38 )

[0255] Formula (Y4): -C(Rn)(H)(Ar)

[0256] In formula (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferred that at least two of Rx1 to Rx3 are methyl groups.

[0257] Among them, it is more preferred that Rx1 to Rx3 are repeating units each independently representing a linear or branched alkyl group, and it is further preferred that Rx1 to Rx3 are repeating units each independently representing a linear alkyl group.

[0258] Two of Rx1 to Rx3 may be bonded to form a monocyclic ring or a polycyclic ring.

[0259] As the alkyl group for Rx1 to Rx3, an alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group, is preferred.

[0260] The cycloalkyl group for Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0261] The cycloalkyl group formed by bonding two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.

[0262] Regarding the cycloalkyl group formed by bonding two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

[0263] Regarding the groups represented by the formulae (Y1) and (Y2), for example, it is preferred that Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0264] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 With R 38 They may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. 36 Preferred is a hydrogen atom.

[0265] In formula (Y4), Ar represents an aromatic hydrocarbon group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0266] The repeating unit having a structure in which the phenolic hydroxyl group is protected by a leaving group that is decomposed and released by an acid (acid-decomposable group) is preferably a repeating unit having a structure in which the hydrogen atom in the phenolic hydroxyl group is protected by a group represented by formulae (Y1) to (Y4).

[0267] As the repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of an acid (acid-decomposable group), a repeating unit represented by the following general formula (AII) is preferred.

[0268] [Chemical formula 18]

[0269]

[0270] In the general formula (AII),

[0271] R 61 , R 62 and R 63 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 62 It can bond with Ar6 to form a ring. In this case, R 62 represents a single bond or an alkylene group.

[0272] X6 represents a single bond, -COO- or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group.

[0273] L6 represents a single bond or an alkylene group.

[0274] Ar6 represents an (n+1) valent aromatic hydrocarbon group, when combined with R 62 When they are bonded to form a ring, they represent an aromatic hydrocarbon group having a valence of (n+2).

[0275] Regarding Y2, when n≥2, each independently represents a hydrogen atom or a group that is dissociated by the action of an acid. Among them, at least one of Y2 represents a group that is dissociated by the action of an acid. The group that is dissociated by the action of an acid as Y2 is preferably a group of formula (Y1) to (Y4).

[0276] n represents an integer of 1 to 4.

[0277] Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). Preferably, the substituent has 8 or less carbon atoms.

[0278] [Chemical formula 19]

[0279]

[0280] [Chemical formula 20]

[0281]

[0282] (Other repeating units)

[0283] The resin (A) may contain other repeating units in addition to the above-mentioned repeating units. Hereinafter, other repeating units that the resin (A) may contain will be described in detail.

[0284] (Repeating unit (a3) ​​having a carboxyl group)

[0285] The resin (A) may further contain a repeating unit (a3) ​​having a carboxyl group in addition to the repeating unit (a1) and the repeating unit (a2).

[0286] The resin (A) contains the repeating unit (a3), so that the dissolution rate during alkali development is further improved.

[0287] As a repeating unit (a3), the repeating unit derived from the following (meth)acrylic acid is mentioned, for example.

[0288] [Chemical formula 21]

[0289]

[0290] The resin (A) may have one type of repeating unit (a3) ​​alone, or may have two or more types thereof simultaneously.

[0291] 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).

[0292] (Repeating unit (a4) having a phenolic hydroxyl group)

[0293] The resin (A) may further contain a repeating unit (a4) having a phenolic hydroxyl group in addition to the repeating unit (a1) and the repeating unit (a2).

[0294] The resin (A) contains the repeating unit (a4), and thus has an excellent dissolution rate during alkali development and excellent etching resistance.

[0295] 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. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (I).

[0296] [Chemical formula 22]

[0297]

[0298] In the formula,

[0299] R 41 , R 42 and R 43 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 42 It can bond with Ar4 to form a ring. In this case, R 42 represents a single bond or an alkylene group.

[0300] X4 represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group.

[0301] L4 represents a single bond or a divalent linking group.

[0302] Ar4 represents an (n+1) valent aromatic hydrocarbon group, when combined with R 42 When they are bonded to form a ring, they represent an aromatic hydrocarbon group having a valence of (n+2).

[0303] n represents an integer of 1-5.

[0304] In order to make the repeating unit represented by the general formula (I) highly polar, it is also preferred that n is an integer of 2 or more or X4 is -COO- or -CONR 64 -.

[0305] As R in the general formula (I) 41 , R 42 and R 43 The alkyl group represented by is preferably an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl, which may have a substituent, more preferably an alkyl group having 8 or less carbon atoms, and further preferably an alkyl group having 3 or less carbon atoms.

[0306] As R in the general formula (I) 41 , R 42 and R 43 The cycloalkyl group represented by may be monocyclic or polycyclic, and preferably is a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl and cyclohexyl, which may have a substituent.

[0307] As R in the general formula (I) 41 , R 42 and R 43 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

[0308] As R in the general formula (I) 41 , R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group represented by 41 , R 42 and R 43 The alkyl group in is the same as the alkyl group.

[0309] Preferred substituents in the above-mentioned groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, urea groups, carbamate groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups and nitro groups, and preferably the substituents have 8 or less carbon atoms.

[0310] Ar4 represents an (n+1)-valent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group when n is 1 may have a substituent, for example, preferably an arylene group having 6 to 18 carbon atoms such as phenylene, tolylene, naphthyl and anthracenyl, or an aromatic hydrocarbon group containing a heterocycle such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole and thiazole.

[0311] As specific examples of the (n+1)-valent aromatic hydrocarbon group when n is an integer of 2 or more, preferably, there can be mentioned groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic hydrocarbon group.

[0312] The (n+1)-valent aromatic hydrocarbon group may further have a substituent.

[0313] Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n+1)-valent aromatic hydrocarbon group may have include: 41 , R 42 and R 43 The alkyl groups mentioned above; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl; and the like.

[0314] As -CONR represented by X4 64 -(R 64 represents a hydrogen atom or an alkyl group) 64 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl, which may have a substituent, and more preferably an alkyl group having 8 or less carbon atoms.

[0315] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0316] The divalent linking group of L4 is preferably an alkylene group, and the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group which may have a substituent.

[0317] Ar4 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and more preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group. Among them, it is preferred that the repeating unit represented by the general formula (I) is a repeating unit derived from hydroxystyrene. That is, Ar4 is preferably a benzene ring group.

[0318] Specific examples of the repeating unit having a phenolic hydroxyl group are shown below, but the present invention is not limited thereto.

[0319] [Chemical formula 23]

[0320]

[0321] The resin (A) may have one type of repeating unit (a4) alone, or may have two or more types thereof simultaneously.

[0322] In the resin (A), the content of the repeating unit (a4) is preferably 40 mol% or more, more preferably 50 mol% or more, and further preferably 60 mol% or more relative to all the repeating units in the resin (A). Furthermore, the content of the repeating unit (a4) is preferably 85 mol% or less, and more preferably 80 mol% or less relative to all the repeating units in the resin (A).

[0323] (Repeating unit (a5))

[0324] The resin (A) may contain at least one repeating unit (a5) selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0325] The lactone structure or sultone structure may have a lactone structure or sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferred. Among them, a lactone structure or a sultone structure in which another ring structure is condensed with the 5- to 7-membered ring lactone structure in the form of a bicyclic structure or a spirocyclic structure, or a lactone structure or a sultone structure in which another ring structure is condensed with the 5- to 7-membered ring sultone structure in the form of a bicyclic structure or a spirocyclic structure is more preferred.

[0326] The resin (A) further preferably contains a repeating unit having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of the following general formulas (SL1-1) to (SL1-3). In addition, the lactone structure or the sultone structure may be directly bonded to the main chain. Preferred structures include lactone structures represented by the general formula (LC1-1), the general formula (LC1-4), the general formula (LC1-5), the general formula (LC1-8), the general formula (LC1-16) or the general formula (LC1-21) or the sultone structure represented by the general formula (SL1-1).

[0327] [Chemical formula 24]

[0328]

[0329] The lactone structure part or the sultone structure part may or may not have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-decomposable groups, preferably alkyl groups having 1 to 4 carbon atoms, cyano groups, or acid-decomposable groups. n2 represents an integer of 0 to 4. When n2 is 2 or more, the multiple substituents (Rb2) may be the same or different. Furthermore, the multiple substituents (Rb2) may be bonded to each other to form a ring.

[0330] As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III) is preferred.

[0331] [Chemical formula 25]

[0332]

[0333] In the above general formula (III),

[0334] A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).

[0335] n is the number of repetitions of the structure represented by -R0-Z-, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R0-Z- does not exist but becomes a single bond.

[0336] R0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are multiple R0 groups, R0 groups independently represent an alkylene group, a cycloalkylene group, or a combination thereof.

[0337] 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 Zs, Zs each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.

[0338] R8 represents a monovalent organic group having a lactone structure or a sultone structure.

[0339] R7 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

[0340] The alkylene group or cycloalkylene group of R0 may have a substituent.

[0341] Z is preferably an ether bond or an ester bond, and more preferably an ester bond.

[0342] The resin (A) may contain a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.

[0343] The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

[0344] [Chemical formula 26]

[0345]

[0346] In the general formula (A-1), R A 1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

[0347] n represents an integer greater than or equal to 0.

[0348] R A 2 represents a substituent. When n is 2 or more, R A 2 Each independently represents a substituent.

[0349] A represents a single bond or a divalent linking group.

[0350] Z represents an atomic group which forms a monocyclic structure or a polycyclic structure together with the group represented by -OC(=O)-O- in the formula.

[0351] It is also preferred that the resin (A) has, as a repeating unit having at least one repeating unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, the repeating units described in paragraphs <0370> to <0414> of US Patent Application Publication No. 2016 / 0070167A1.

[0352] The resin (A) may have one type of repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may have two or more types thereof.

[0353] Specific examples of monomers corresponding to the repeating unit represented by the general formula (III) and specific examples of monomers corresponding to the repeating unit represented by the general formula (A-1) are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to R7 in the general formula (III) and R in the general formula (A-1). A 1 In the case of methyl, R7 and R A 1 It may be arbitrarily substituted with a hydrogen atom, a halogen atom or a monovalent organic group.

[0354] [Chemical formula 27]

[0355]

[0356] In addition to the above-mentioned monomers, monomers shown below can also be preferably used as a raw material of the resin (A).

[0357] [Chemical formula 28]

[0358]

[0359] The content of at least one repeating unit selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure contained in the resin (A) (the total of a plurality of repeating units having at least one repeating unit selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure) is preferably 5 to 30 mol %, more preferably 10 to 30 mol %, and further preferably 20 to 30 mol % relative to all repeating units in the resin (A).

[0360] The resin (A) may have various repeating structural units in addition to the above-mentioned repeating structural units for the purpose of adjusting dry etching resistance, compatibility with standard developer, substrate adhesion, resist profile, or generally required properties of resists, i.e., resolution, heat resistance, sensitivity, etc.

[0361] Examples of such a repeating structural unit include repeating structural units corresponding to predetermined monomers, but the repeating structural units are not limited thereto.

[0362] Examples of the predetermined monomer include compounds having one addition-polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters.

[0363] In addition, an addition-polymerizable unsaturated compound copolymerizable with the monomer corresponding to the above-mentioned various repeating structural units may also be used.

[0364] In the resin (A), the molar ratio of each repeating structural unit can be appropriately set in order to adjust various properties.

[0365] The repeating units of the resin (A) may all be composed of (meth)acrylate repeating units. In this case, any of a resin in which all repeating units are methyl acrylate repeating units, a resin in which all repeating units are acrylate repeating units, and a resin in which all repeating units are based on methyl acrylate repeating units and acrylate repeating units can be used, and the acrylate repeating units preferably account for 50 mol% or less of all repeating units of the resin (A).

[0366] (Repeating unit having an aromatic ring)

[0367] The resin (A) preferably contains a repeating unit having an aromatic ring. That is, at least any one of the repeating units in the resin (A) is preferably a repeating unit having an aromatic ring.

[0368] From the viewpoint of achieving better etching resistance, the content of repeating units having an aromatic ring in the resin (A) is, for example, 40 mol% or more, preferably 55 mol% or more, and more preferably 60 mol% or more relative to all repeating units in the resin (A). The upper limit is not particularly limited, and is, for example, 97 mol% or less, preferably 85 mol% or less, and more preferably 80 mol% or less.

[0369] (Polymerization method of resin (A))

[0370] The resin (A) can be synthesized by a conventional method (e.g., free radical polymerization). As general synthesis methods, for example, there can be mentioned (1) a general polymerization method in which a monomer species and an initiator are dissolved in a solvent and then polymerized by heating, (2) a dropwise polymerization method in which a solution containing a monomer species and an initiator is added dropwise to a heated solvent over 1 to 10 hours, and the dropwise polymerization method (2) is preferred.

[0371] As the reaction solvent during polymerization, for example, 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, amides such as dimethylformamide and dimethylacetamide, and propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and cyclohexanone described later can be cited to dissolve the solvent of the composition of the present invention. As the reaction solvent during polymerization, it is preferably used the same solvent as the solvent used in the composition of the present invention. Thus, it is possible to suppress the generation of particulate matter during storage.

[0372] The polymerization reaction is preferably carried out under an inert gas environment such as nitrogen and argon. It is preferred that a commercially available free radical initiator (e.g., azo initiators and peroxides, etc.) be used as a polymerization initiator in the polymerization reaction. As a free radical initiator, an azo initiator is preferred, and an azo initiator having an ester group, a cyano group or a carboxyl group is more preferred. As such an azo initiator, for example, azobisisobutyronitrile, azobisdimethylvaleronitrile and dimethyl 2,2'-azobis(2-methylpropionate) can be cited.

[0373] As mentioned above, a polymerization initiator can be added arbitrarily in the polymerization reaction. The method for adding the polymerization initiator to the system is not particularly limited, and it can be a method of adding it in general or in a method of adding it in multiple times. During 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, and more preferably 60 to 100°C. After the reaction is completed, the polymer is recovered by a method such as a method of putting it into a solvent and recovering the powder or solid content.

[0374] The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 30,000, and further preferably 3,000 to 25,000. The degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further preferably 1.1 to 2.0.

[0375] The resin (A) may be used alone or in combination of two or more.

[0376] In the composition of the present invention, the content of resin (A) is usually more than 20% by mass relative to the total solid content, preferably more than 40% by mass, more preferably more than 60% by mass, and further preferably more than 80% by mass. The upper limit is not particularly limited, but is preferably less than 99.5% by mass, more preferably less than 99% by mass, and further preferably less than 98% by mass.

[0377] (Solid content concentration)

[0378] The solid content concentration of the photosensitive ray or radiation-sensitive resin composition of the present invention is preferably 10% by mass or more. As a result, for example, a pattern of a thick film having a film thickness of 1 μm or more (preferably 10 μm or more) is easily formed. In addition, the solid content concentration refers to the mass percentage of the mass of other resist components (components that can constitute the resist film) excluding the solvent relative to the total mass of the composition of the present invention.

[0379] <Compounds that generate acid upon irradiation with actinic rays or radiation (photoacid generators)>

[0380] [Compound represented by general formula (P-1)]

[0381] The composition of the present invention contains a compound represented by the following general formula (P-1) as a compound that generates an acid upon irradiation with actinic rays or radiation.

[0382] [Chemical formula 29]

[0383]

[0384] In the above general formula (P-1),

[0385] Q1 means including S + Ring.

[0386] Ring Q1 is a 4-membered ring, a 5-membered ring or a 6-membered ring, wherein Ring Q1 may form a condensed ring with other rings.

[0387] As ring elements, ring Q1 has at least 2 carbon atoms, + The atoms to which the ring elements are directly bonded are carbon atoms.

[0388] R P1 ~R P5 R each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. P1 ~R P5 At least two of them may be bonded to form a ring.

[0389] Z - Represents a non-nucleophilic anion.

[0390] In the above general formula (P-1), Q1 represents a + The ring represented by Q1 may be an alicyclic ring (non-aromatic ring) or an aromatic ring, but is preferably a non-aromatic ring.

[0391] The ring represented by Q1 is a 4-membered ring, a 5-membered ring or a 6-membered ring, and is preferably a 6-membered ring.

[0392] The ring represented by Q1 may form a condensed ring with other rings. As other rings, it may be an alicyclic ring (non-aromatic ring) or an aromatic ring, but is preferably a non-aromatic ring. Other rings are preferably 4-membered rings, 5-membered rings or 6-membered rings, more preferably 6-membered rings.

[0393] Ring Q1 may have a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 6 carbon atoms) and an electron withdrawing group (eg, an acyl group, a sulfonate group).

[0394] As ring elements, ring Q1 has at least 2 carbon atoms, + The atoms to which the ring elements are directly bonded are carbon atoms.

[0395] As ring elements, ring Q1 preferably has, in addition to S + When the hetero atom referred to herein is a hetero atom with a valence of tri or higher (for example, a nitrogen atom), it includes a hetero atom bonded to a hydrogen atom or a substituent.

[0396] As in addition to S + The hetero atom other than includes an oxygen atom, a nitrogen atom, a sulfur atom and the like, and an oxygen atom or a nitrogen atom is preferred.

[0397] In the above general formula (P-1), R P1 ~R P5 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group.

[0398] As R P1 ~R P5 The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom.

[0399] As R P1 ~R P5 The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6. Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, etc. The alkyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom.

[0400] As R P1 ~R P5The number of carbon atoms of the aryl group is preferably 6 to 10. Examples of the aryl group include a phenyl group and the like. The aryl group may have a substituent.

[0401] As R P1 ~R P5 The heteroaryl group is not particularly limited, but is preferably an aromatic heterocyclic group containing at least one of a sulfur atom, a nitrogen atom and an oxygen atom as a hetero atom in the ring element. The heteroaryl group may have a substituent.

[0402] As R P1 ~R P5 The alkoxy group may be straight-chain or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6. Examples of the alkoxy group include methoxy, ethoxy, and tert-butoxy. The alkoxy group may have a substituent, and the substituent is not particularly limited, and examples thereof include alkoxy (e.g., an alkoxy group having 1 to 6 carbon atoms) or cycloalkyl (e.g., a cycloalkyl group having 5 to 10 carbon atoms).

[0403] Preferred R P1 ~R P5 At least one of them represents a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group, more preferably represents a hydroxyl group, an alkyl group or an alkoxy group, and further preferably represents an alkoxy group.

[0404] R P1 ~R P5 At least two of them may be bonded to form a ring. When forming a ring, preferably R P1 ~R P5 Two adjacent bonds in the amine group are bonded to form a ring. The formed ring may be an aliphatic ring or an aromatic ring. Furthermore, the formed ring may be a hydrocarbon ring or a heterocyclic ring.

[0405] In the above general formula (P-1), Z - Represents a non-nucleophilic anion.

[0406] Z - Although not particularly limited, anions represented by any of the following general formulae (Z1) to (Z4) are preferred.

[0407] [Chemical formula 30]

[0408]

[0409] In the general formula (Z1), R Z1 It represents an alkyl group.

[0410] [Chemical formula 31]

[0411]

[0412] In the general formula (Z2),

[0413] Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. A plurality of Xf may be the same or different.

[0414] R Z2 and R Z3 Each independently represents a hydrogen atom, a fluorine atom or an alkyl group. Z2 and R Z3 They can be the same or different.

[0415] L Z1 represents a divalent linking group, and when there are multiple L Z1 It can be the same or different.

[0416] A Z1 It represents an organic group containing a ring structure.

[0417] x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

[0418] [Chemical formula 32]

[0419]

[0420] In the general formulae (Z3) and (Z4), Rb3 to Rb7 each independently represent an alkyl group, a cycloalkyl group or an aryl group. Rb3 and Rb4 may be bonded to form a ring. Rb5 and Rb6 may be bonded to form a ring.

[0421] In the general formula (Z1), R Z1 represents an alkyl group, which may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6. Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, etc. The alkyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom, preferably a fluorine atom.

[0422] In the general formula (Z2), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. A plurality of Xf may be the same or different. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0423] 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, Xf is more preferably a fluorine atom.

[0424] R Z2 and R Z3Each independently represents a hydrogen atom, a fluorine atom or an alkyl group.

[0425] By R Z2 and R Z3 The alkyl group represented by may be linear or branched. The number of carbon atoms of the above alkyl group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. Examples of the above alkyl group include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, and the like. The above alkyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom, preferably a fluorine atom. The preferred range when the alkyl group represents an alkyl group substituted with at least one fluorine atom is the same as the preferred range described in the above Xf.

[0426] L Z1 It represents a divalent linking group.

[0427] Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene (preferably having 1 to 6 carbon atoms), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms), and divalent linking groups obtained by combining a plurality of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, or -NHCO-alkylene- is preferred, and -COO-, -OCO-, -CONH-alkylene-, -SO2-, -COO-alkylene-, or -OCO-alkylene- is more preferred, and -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene-, or -OCO-alkylene- is more preferred.

[0428] A Z1 represents an organic group containing a cyclic structure. Among them, a cyclic organic group is preferred.

[0429] Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.

[0430] The alicyclic group may be monocyclic or polycyclic. As monocyclic alicyclic groups, for example, monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl can be cited. As polycyclic alicyclic groups, for example, polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl can be cited. Among them, preferred alicyclic groups with bulky structures having more than 7 carbon atoms such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl are cited.

[0431] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl and anthracenyl.

[0432] The heterocyclic group may be monocyclic or polycyclic. The polycyclic group can further inhibit the diffusion of the acid. In addition, the heterocyclic group may or may not be aromatic. As heterocyclic rings with aromaticity, for example, furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings and pyridine rings may be mentioned. As heterocyclic rings without aromaticity, for example, tetrahydropyran rings, lactone rings, sultone rings and decahydroisoquinoline rings may be mentioned. As examples of lactone rings and sultone rings, lactone structures and sultone structures exemplified in the aforementioned resins may be mentioned. As heterocyclic rings in heterocyclic groups, furan rings, thiophene rings, pyridine rings or decahydroisoquinoline rings are particularly preferred.

[0433] The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic or spirocyclic, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a carbamate group, a urea group, a thioether group, a sulfonamide group and a sulfonate group. In addition, the carbon (carbon that contributes to the formation of the ring) constituting the cyclic organic group may be a carbonyl carbon.

[0434] As the anion represented by the general formula (Z2), SO3 is preferred. - -CF2-CH2-OCO-(L Z1 )q'-A Z1 、SO3 - -CF2-CHF-CH2-OCO-(L Z1 )q'-A Z1 、SO3 - -CF2-COO-(L Z1 )q'-A Z1 、SO3 - -CF2-CF2-CH2-CH2-(L Z1 ) Z1 、SO3 - -CF2-CH(CF3)-OCO-(L Z1 )q'-A Z1 Among them, L Z1 , z and A Z1 They are the same as the anions in the general formula (Z2). q' represents an integer of 0-10.

[0435] In the general formulae (Z3) and (Z4), Rb3 to Rb7 each independently represent an alkyl group, a cycloalkyl group or an aryl group. The alkyl group may be any of a linear group and a branched group, and preferably has 1 to 12 carbon atoms. The cycloalkyl group may be any of a monocyclic group, a polycyclic group or a spirocyclic group, and preferably has 3 to 20 carbon atoms. The aryl group preferably has 6 to 14 carbon atoms.

[0436] Rb3 and Rb4 may be bonded to form a ring. Rb5 and Rb6 may be bonded to form a ring.

[0437] The following shows Z - Specific examples of, but are not limited to them.

[0438] [Chemical formula 33]

[0439]

[0440] [Chemical formula 34]

[0441]

[0442] The compound represented by the general formula (P-1) is preferably a compound represented by the following general formula (P-2).

[0443] [Chemical formula 35]

[0444]

[0445] In the above general formula (P-2),

[0446] R P1 ~R P5 R each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group. P1 ~R P5 At least two of them may be bonded to form a ring.

[0447] R P6 ~R P9 Each independently represents a hydrogen atom or a substituent.

[0448] m1 and m2 each independently represent 1 or 2.

[0449] R P6 ~R P9 When there are plural of each, they may be the same or different.

[0450] When m1 represents 2, 2 R P6 They may be bonded to each other to form a ring.

[0451] When m2 represents 2, 2 R P8 They may be bonded to each other to form a ring.

[0452] M1 represents a heteroatom or -CR P10 R P11 -. R P10 and R P11 Each independently represents a hydrogen atom or a substituent.

[0453] Z - Represents a non-nucleophilic anion.

[0454] In the above general formula (P-2), R P1 ~R P5 , Z - Respectively with R in the above general formula (P-1) P1 ~R P5 , Z - The meanings are the same, and the preferred ranges are also the same.

[0455] In the above general formula (P-2), R P6 ~R P9 Each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 6 carbon atoms).

[0456] m1 and m2 each independently represent 1 or 2, and preferably represent 2.

[0457] R P6 ~R P9 When there are plural of each, they may be the same or different.

[0458] When m1 represents 2, 2 R P6 They may be bonded to each other to form a ring. The formed ring may be an alicyclic ring (non-aromatic ring) or an aromatic ring, but is preferably a non-aromatic ring. The formed ring is preferably a 4-membered ring, a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring.

[0459] When m2 represents 2, 2 R P8 They may be bonded to each other to form a ring. The formed ring may be an alicyclic ring (non-aromatic ring) or an aromatic ring, but is preferably a non-aromatic ring. The formed ring is preferably a 4-membered ring, a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring.

[0460] In the above general formula (P-2), M1 represents a heteroatom or -CR P10 R P11 -. R P10 and R P11 Each independently represents a hydrogen atom or a substituent. Preferably, M1 represents a heteroatom.

[0461] When M1 represents a heteroatom, as the heteroatom, an oxygen atom, a nitrogen atom or a sulfur atom is preferred, and an oxygen atom or a nitrogen atom is more preferred. When the heteroatom can have a substituent, it may have a substituent. For example, when the heteroatom is a nitrogen atom, as the substituent, a group that reduces the basicity of the nitrogen atom is preferred, and electron-withdrawing groups such as acyl groups and sulfonate groups can be cited. As the acyl group, an acyl group having 1 to 10 carbon atoms is preferred, and an acyl group having 1 to 5 carbon atoms is more preferred. As the sulfonate group, a sulfonate group having 1 to 10 carbon atoms is preferred, and a sulfonate group having 1 to 5 carbon atoms is more preferred.

[0462] The compound represented by the general formula (P-1) is preferably a compound represented by the following general formula (P-3).

[0463] [Chemical formula 36]

[0464]

[0465] In the above general formula (P-3),

[0466] R P1 , R P2 , R P4 and R P5 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group.

[0467] R P6 ~R P9 Each independently represents a hydrogen atom or a substituent.

[0468] m1 and m2 each independently represent 1 or 2.

[0469] R P6 ~R P9 When there are plural of each, they may be the same or different.

[0470] When m1 represents 2, 2 R P6 They may be bonded to each other to form a ring.

[0471] When m2 represents 2, 2 R P8 They may be bonded to each other to form a ring.

[0472] M1 represents a heteroatom or -CR P10 R P11 -. R P10 and R P11 Each independently represents a hydrogen atom or a substituent.

[0473] R P12 represents a hydrogen atom or an alkyl group.

[0474] R P1 , R P2 , R P4, R P5 and R P12 At least two of them may be bonded to form a ring.

[0475] Z - Represents a non-nucleophilic anion.

[0476] In the above general formula (P-3), R P1 , R P2 , R P4 , R P5 , Z - Respectively with R in the above general formula (P-1) P1 , R P2 , R P4 , R P5 , Z - The meanings are the same, and the preferred ranges are also the same.

[0477] In the above general formula (P-3), R P6 ~R P9 , m1, m2, M1 are respectively the same as R in the above general formula (P-2) P6 ~R P9 , m1, m2, and M1 have the same meaning and the same preferred range.

[0478] In the above general formula (P-3), R P12 represents a hydrogen atom or an alkyl group.

[0479] As R P12 When the alkyl group is an alkyl group, the alkyl group may be linear or branched, and is preferably linear. P12 When an alkyl group is represented, the number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, and a tert-butyl group. The alkyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include an alkoxy group (e.g., an alkoxy group having 1 to 6 carbon atoms) or a cycloalkyl group (e.g., a cycloalkyl group having 5 to 10 carbon atoms).

[0480] R P1 , R P2 , R P4 , R P5 and R P12 At least two of them may be bonded to form a ring. When forming a ring, preferably R P1 , R P2 , R P4 , R P5 and R P12 Two adjacent bonds in the amine group are bonded to form a ring. The formed ring may be an aliphatic ring or an aromatic ring. Furthermore, the formed ring may be a hydrocarbon ring or a heterocyclic ring.

[0481] The compound represented by the general formula (P-1) is particularly preferably a compound represented by the following general formula (P-4) or (P-5).

[0482] [Chemical formula 37]

[0483]

[0484] [Chemical formula 38]

[0485]

[0486] In the above general formulas (P-4) and (P-5),

[0487] R P1 , R P2 , R P4 and R P5 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group.

[0488] R P6 ~R P9 Each independently represents a hydrogen atom or a substituent.

[0489] There are multiple R P6 ~R P9 They can be the same or different.

[0490] 2 R's P6 They may be bonded to each other to form a ring.

[0491] 2 R's P8 They may be bonded to each other to form a ring.

[0492] M1 represents a heteroatom or -CR P10 R P11 -. R P10 and R P11 Each independently represents a hydrogen atom or a substituent.

[0493] R P12 represents a hydrogen atom or a substituent.

[0494] R P1 , R P2 , R P4 , R P5 and R P12 At least two of them may be bonded to form a ring.

[0495] Z - Represents a non-nucleophilic anion.

[0496] In the above general formula (P-5), R P13 represents a hydrogen atom or a substituent.

[0497] In the above general formulas (P-4) and (P-5), R P1 , R P2 , R P4 , R P5 , Z - Respectively with R in the above general formula (P-1) P1 , R P2 , R P4 , R P5 , Z - The meanings are the same, and the preferred ranges are also the same.

[0498] In the above general formulas (P-4) and (P-5), R P6 ~R P9 Respectively with R in the above general formula (P-2) P6 ~R P9 The meanings are the same, and the preferred ranges are also the same.

[0499] In the above general formulas (P-4) and (P-5), R P12 and R in the above general formula (P-3) P12 The meanings are the same, and the preferred ranges are also the same.

[0500] In the above general formula (P-5), R P13 represents a hydrogen atom or a substituent.

[0501] R P13 When a substituent is represented, there is no particular limitation on the substituent, but a group that reduces the basicity of the nitrogen atom is preferred, and examples thereof include electron-withdrawing groups such as an acyl group and a sulfonate group. As the acyl group, an acyl group having 1 to 10 carbon atoms is preferred, and an acyl group having 1 to 5 carbon atoms is more preferred. As the sulfonate group, a sulfonate group having 1 to 10 carbon atoms is preferred, and a sulfonate group having 1 to 5 carbon atoms is more preferred.

[0502] Specific examples of the compound represented by the general formula (P-1) are shown below, but the compound is not limited to these.

[0503] [Chemical formula 39]

[0504]

[0505] [Chemical formula 40]

[0506]

[0507] [Chemical formula 41]

[0508]

[0509] The compound represented by the general formula (P-1) can be synthesized by a known method (for example, the method described in JP-A-2014-199389).

[0510] The molecular weight of the compound represented by the general formula (P-1) is preferably 3,000 or less, more preferably 2,000 or less, and further preferably 1,000 or less.

[0511] The compound represented by the general formula (P-1) may be used alone or in combination of two or more.

[0512] In the composition of the present invention, the content of the compound represented by the general formula (P-1) (the total when there are two or more) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, further preferably 1 to 20% by mass, and particularly preferably 1 to 15% by mass, based on the total solid content of the composition.

[0513] [Photoacid generator other than the compound represented by the general formula (P-1)]

[0514] The composition of the present invention may further contain, in addition to the compound represented by the general formula (P-1), a photoacid generator other than the compound represented by the general formula (P-1), as a compound that generates an acid upon irradiation with actinic rays or radiation.

[0515] Examples of the photoacid generator other than the compound represented by the general formula (P-1) include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, azodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.

[0516] As a photoacid generator other than the compound represented by the general formula (P-1), a known compound that generates an acid by irradiation with actinic rays or radiation can be used alone or as a mixture thereof. For example, known compounds disclosed in paragraphs

[0125] to

[0319] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs <0086> to <0094> of U.S. Patent Application Publication No. 2015 / 0004544A1, and paragraphs <0323> to <0402> of U.S. Patent Application Publication No. 2016 / 0237190A1 can be preferably used.

[0517] As the photoacid generator other than the compound represented by the general formula (P-1), for example, a compound represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) is preferable.

[0518] [Chemical formula 42]

[0519]

[0520] In the above general formula (ZI),

[0521] R 201 , R 202 and R 203 Each independently represents an organic group.

[0522] As R 201 , R 202 and R 203 The organic group has usually 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0523] And, R 201 ~R 203 Two of them 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. 201 ~R 203 The group that can be formed by two of them being bonded to each other includes an alkylene group (e.g., a butylene group and a pentylene group) and -CH2-CH2-O-CH2-CH2-.

[0524] Z - represents an anion (preferably a non-nucleophilic anion).

[0525] Preferred embodiments of the cation in the general formula (ZI) include corresponding groups in the compounds (ZI-1), (ZI-2), the compounds represented by the general formula (ZI-3) (compound (ZI-3)) and the compounds represented by the general formula (ZI-4) (compound (ZI-4)) described later.

[0526] In addition, the photoacid generator other than the compound represented by the general formula (P-1) may be a compound having a plurality of structures represented by the general formula (ZI). For example, R of the compound represented by the general formula (ZI) 201 ~R 203 and R of another compound represented by the general formula (ZI) 201 ~R 203 At least one of them may be a compound having a structure bonded via a single bond or a linking group.

[0527] First, compound (ZI-1) will be described.

[0528] Compound (ZI-1) is the above general formula (ZI) wherein R 201 ~R 203 An arylsulfonium compound in which at least one of the groups is an aryl group, that is, a compound having an arylsulfonium cation.

[0529] In arylsulfonium compounds, R 201 ~R 203 can be aryl, R 201 ~R 203 A part of alkyl may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.

[0530] Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0531] As the aryl group contained in the arylsulfonium compound, phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group may also be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom or a sulfur atom. As the heterocyclic structure, pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue and benzothiophene residue can be cited. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

[0532] The alkyl group or cycloalkyl group which the arylsulfonium compound has as required is a linear alkyl group having 1 to 15 carbon atoms, preferably a branched alkyl group having 3 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl and cyclohexyl.

[0533] R 201 ~R 203 The aryl group, alkyl group and cycloalkyl group may each independently have an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group or a phenylthio group as a substituent.

[0534] Next, compound (ZI-2) is described.

[0535] Compound (ZI-2) is a compound having the formula (ZI) wherein R 201 ~R 203 Each independently represents a compound having an organic group without an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.

[0536] As R 201 ~R 203 The organic group having no aromatic ring usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0537] R 201 ~R 203Each independently is preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, and further preferably a linear or branched 2-oxoalkyl group.

[0538] As R 201 ~R 203 The alkyl group and the cycloalkyl group preferably include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl and pentyl) and a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl).

[0539] R 201 ~R 203 It may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.

[0540] Next, compound (ZI-3) is described.

[0541] [Chemical formula 43]

[0542]

[0543] In the general formula (ZI-3), M represents an alkyl group, a cycloalkyl group or an aryl group, and when it has a ring structure, the ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond and a carbon-carbon double bond. 6c and R 7c R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. 6c With R 7c They may be bonded to form a ring. x and R y R each independently represents an alkyl group, a cycloalkyl group or an alkenyl group. x and R y can be bonded to form a ring. And, selected from M, R 6c and R 7c At least two of Z may be bonded to form a ring structure, and the ring structure may contain a carbon-carbon double bond. - Represents an anion.

[0544] In the general formula (ZI-3), the alkyl group and cycloalkyl group represented by M are preferably a straight-chain alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), a branched-chain alkyl group having 3 to 15 carbon atoms (preferably 3 to 10 carbon atoms), or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Specifically, there can be mentioned a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and a norbornyl group.

[0545] As the aryl group represented by M, phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom or a sulfur atom, etc. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.

[0546] The above-mentioned M may further have a substituent (for example, a substituent T). In this embodiment, for example, M may include a benzyl group.

[0547] In addition, when M has a ring structure, the ring structure may include at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.

[0548] As R 6c and R 7c The alkyl group, cycloalkyl group and aryl group represented by may be the same as those for M, and the preferred embodiments thereof are also the same. 6c With R 7c They may be bonded to form a ring.

[0549] As R 6c and R 7c Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0550] As R x and R y Examples of the alkyl group and cycloalkyl group represented by include the same groups as those mentioned above for M, and preferred embodiments thereof are also the same.

[0551] As R x and R y The alkenyl group represented by is preferably an allyl group or a vinyl group.

[0552] The above R x and R y It may further have a substituent (eg, a substituent T). x and R y Examples thereof include 2-oxoalkyl and alkoxycarbonylalkyl.

[0553] As R x and R y Examples of the 2-oxoalkyl group represented by include groups having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), and specific examples include 2-oxopropyl and 2-oxobutyl.

[0554] As R x and R y Examples of the alkoxycarbonylalkyl group represented by include groups having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). x With R yThey may be bonded to form a ring.

[0555] R x With R y The ring structure formed by the mutual connection may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbon-carbon double bond.

[0556] In the general formula (ZI-3), M and R 6c The two may be bonded to form a ring structure, and the formed ring structure may contain a carbon-carbon double bond.

[0557] Among them, the compound (ZI-3) is preferably the compound (ZI-3A).

[0558] The compound (ZI-3A) is represented by the following general formula (ZI-3A) and has a phenacylsulfonium salt structure.

[0559] [Chemical formula 44]

[0560]

[0561] In the general formula (ZI-3A),

[0562] R 1c ~R 5c Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.

[0563] As R 6c and R 7c , which has the same meaning as R in the above general formula (ZI-3) 6c and R 7c The same, the preferred mode is also the same.

[0564] As R x and R y , which has the same meaning as R in the above general formula (ZI-3) x and R y The same, the preferred mode is also the same.

[0565] R 1c ~R 5c Any two or more of R x With R y Each of them may be bonded to form a ring structure, and the ring structure may independently contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond. 5c and R 6c , R 5c and R xEach of them may be bonded to form a ring structure, and the ring structure may each independently contain a carbon-carbon double bond. 6c With R 7c They may be bonded to each other to form a ring structure.

[0566] Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0567] As R 1c ~R 5c Any two or more of R 6c With R 7c and R x With R y Examples of the group formed by bonding include a butylene group and a pentylene group.

[0568] As R 5c With R 6c and R 5c With R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0569] Zc - Represents an anion.

[0570] Next, compound (ZI-4) is described.

[0571] The compound (ZI-4) is represented by the following general formula (ZI-4).

[0572] [Chemical formula 45]

[0573]

[0574] In the general formula (ZI-4),

[0575] l represents an integer from 0 to 2.

[0576] r represents an integer from 0 to 8.

[0577] R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.

[0578] R 14 When there are plural groups, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.

[0579] R 15 Each of R independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. 15 They may be bonded to each other to form a ring.

[0580] 2 R's 15 When they are bonded to each other to form a ring, heteroatoms such as oxygen atoms and nitrogen atoms may be contained in the ring skeleton. 15 They are alkylene groups, which are bonded to each other to form a ring structure.

[0581] Z - Represents an anion.

[0582] In the general formula (ZI-4), R 13 , R 14 and R 15 The alkyl group is linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. As the alkyl group, a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, or the like is more preferred.

[0583] Next, general formulae (ZII) and (ZIII) are described.

[0584] In the general formulae (ZII) and (ZIII), R 204 ~R 207 Each independently represents an aryl group, an alkyl group or a cycloalkyl group.

[0585] As R 204 ~R 207 R is an aryl group, preferably a phenyl group or a naphthyl group, more preferably a phenyl group. 204 ~R 207 The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom or a sulfur atom. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran and benzothiophene.

[0586] As R 204 ~R 207 The alkyl group and the cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl) or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0587] R 204 ~R 207 The aryl group, alkyl group and cycloalkyl group of R may each independently have a substituent. 204 ~R 207The aryl group, alkyl group and cycloalkyl group may have a substituent, for example, an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group.

[0588] Z - Represents an anion.

[0589] As Z in the general formula (ZI) - , Z in the general formula (ZII) - , Z in the general formula (ZI-3) - , Zc in the general formula (ZI-3A) - and Z in the general formula (ZI-4) - , preferably an anion represented by the following general formula (3).

[0590] [Chemical formula 46]

[0591]

[0592] In general formula (3),

[0593] o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0594] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0595] 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, Xf is more preferably a fluorine atom.

[0596] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are plural R4 and R5, R4 and R5 may be the same or different.

[0597] The alkyl group represented by R4 and R5 may have a substituent, and preferably has a carbon number of 1 to 4. R4 and R5 are preferably a hydrogen atom.

[0598] 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).

[0599] L represents a divalent linking group. When there are plural L, each L may be the same or different.

[0600] Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene (preferably having 1 to 6 carbon atoms), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms), and divalent linking groups obtained by combining a plurality of these. Among them, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, or -NHCO-alkylene- is preferred, and -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene-, or -OCO-alkylene- is more preferred.

[0601] W represents an organic group including a cyclic structure. Among them, a cyclic organic group is preferred.

[0602] Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.

[0603] The alicyclic group may be monocyclic or polycyclic. As monocyclic alicyclic groups, for example, monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl can be cited. As polycyclic alicyclic groups, for example, polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl can be cited. Among them, preferred alicyclic groups with bulky structures having more than 7 carbon atoms such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl are cited.

[0604] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl and anthracenyl.

[0605] The heterocyclic group may be monocyclic or polycyclic. The polycyclic group can further inhibit the diffusion of the acid. In addition, the heterocyclic group may or may not be aromatic. As heterocyclic rings with aromaticity, for example, furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings and pyridine rings may be mentioned. As heterocyclic rings without aromaticity, for example, tetrahydropyran rings, lactone rings, sultone rings and decahydroisoquinoline rings may be mentioned. As examples of lactone rings and sultone rings, lactone structures and sultone structures exemplified in the aforementioned resins may be mentioned. As heterocyclic rings in heterocyclic groups, furan rings, thiophene rings, pyridine rings or decahydroisoquinoline rings are particularly preferred.

[0606] The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic or spirocyclic, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a carbamate group, a urea group, a thioether group, a sulfonamide group and a sulfonate group. In addition, the carbon (carbon that contributes to the formation of the ring) constituting the cyclic organic group may be a carbonyl carbon.

[0607] As the anion represented by the general formula (3), SO3 is preferred. - -CF2-CH2-OCO-(L)q'-W、SO3 - -CF2-CHF-CH2-OCO-(L)q'-W、SO3 - -CF2-COO-(L)q'-W、SO3 - -CF2-CF2-CH2-CH2-(L)qW, SO3 - -CF2-CH(CF3)-OCO-(L)q'-W. Here, L, q and W are the same as those in the general formula (3). q' represents an integer of 0 to 10.

[0608] In one embodiment, Z in the general formula (ZI) is - , Z in the general formula (ZII) - , Z in the general formula (ZI-3) - , Zc in the general formula (ZI-3A) - and Z in the general formula (ZI-4) - , anions represented by the following general formula (4) are also preferred.

[0609] [Chemical formula 47]

[0610]

[0611] In general formula (4),

[0612] X B1 and X B2 Each independently represents a hydrogen atom or a monovalent organic group having no fluorine atom. B1 and X B2 Preferred is a hydrogen atom.

[0613] X B3 and X B4 Each independently represents a hydrogen atom or a monovalent organic group. B3 and X B4 At least one of them is preferably a fluorine atom or a monovalent organic group having a fluorine atom, and X B3 and X B4More preferably, both of X and X are fluorine atoms or monovalent organic groups having fluorine atoms. B3 and X B4 Both are more preferably alkyl groups substituted with fluorine atoms.

[0614] L, q and W are the same as those in the general formula (3).

[0615] As Z in the general formula (ZI) - , Z in the general formula (ZII) - , Z in the general formula (ZI-3) - , Zc in the general formula (ZI-3A) - and Z in the general formula (ZI-4) - , may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted by a branched alkyl group or a cycloalkyl group.

[0616] As Z in the general formula (ZI) - , Z in the general formula (ZII) - , Z in the general formula (ZI-3) - , Zc in the general formula (ZI-3A) - and Z in the general formula (ZI-4) - Also preferred are aromatic sulfonic acid anions represented by the following general formula (SA1).

[0617] [Chemical formula 48]

[0618]

[0619] In formula (SA1),

[0620] Ar represents an aryl group, and may further have a substituent other than the sulfonic acid anion and the -(DB) group. Examples of the substituent that may further have include a fluorine atom and a hydroxyl group.

[0621] n represents an integer greater than or equal to 0. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0622] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate group, an ester group, and a group composed of a combination of two or more thereof.

[0623] B represents a hydrocarbon group.

[0624] Preferably, D is a single bond and B is an aliphatic hydrocarbon structure. More preferably, B is an isopropyl group or a cyclohexyl group.

[0625] Preferred examples of the sulfonium cation in the general formula (ZI) and the iodonium cation in the general formula (ZII) are shown below.

[0626] [Chemical formula 49]

[0627]

[0628] The anion Z in the general formula (ZI) and the general formula (ZII) - , Z in the general formula (ZI-3) - , Zc in the general formula (ZI-3A) - and Z in the general formula (ZI-4) - The preferred example is the same as Z in the compound represented by the general formula (P-1). - same.

[0629] The above-mentioned cations and anions can be used as the photoacid generator in any combination.

[0630] The photoacid generator other than the compound represented by the general formula (P-1) may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Furthermore, the low molecular weight compound and the incorporation in a part of the polymer may be used simultaneously.

[0631] The photoacid generator other than the compound represented by the general formula (P-1) is preferably in the form of a low molecular weight compound.

[0632] When the photoacid generator other than the compound represented by the general formula (P-1) is a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and further preferably 1,000 or less.

[0633] When the photoacid generator other than the compound represented by the general formula (P-1) is incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or in a resin different from the resin (A).

[0634] The photoacid generator other than the compound represented by the general formula (P-1) may be used alone or in combination of two or more.

[0635] When the composition of the present invention contains a photoacid generator other than the compound represented by the general formula (P-1), the content of the photoacid generator other than the compound represented by the general formula (P-1) (the total when there are two or more) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, further preferably 1 to 20% by mass, and particularly preferably 1 to 15% by mass based on the total solid content of the composition.

[0636] When a compound represented by the above general formula (ZI-3) or (ZI-4) is contained as a photoacid generator other than the compound represented by the general formula (P-1), the content of the photoacid generator other than the compound represented by the general formula (P-1) contained in the composition (the total when there are two or more) is preferably 1 to 35% by mass, more preferably 1 to 30% by mass, based on the total solid content of the composition.

[0637] <Acid diffusion control agent>

[0638] The composition of the present invention preferably contains an acid diffusion controller. The acid diffusion controller acts as a quencher that captures the acid generated from the photoacid generator during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed portion caused by the excess acid generation. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappears by irradiation with actinic rays or radiation, an onium salt (DC) that becomes a relatively weak acid relative to the acid generator, a low molecular weight compound (DD) having a nitrogen atom and a group that is separated by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cationic portion can be used as an acid diffusion controller. In the composition of the present invention, a known acid diffusion controller can be appropriately used. For example, known compounds disclosed in paragraphs <0627> to <0664> of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs <0095> to <0187> of U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs <0403> to <0423> of U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs <0259> to <0328> of U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used as the acid diffusion controller.

[0639] As the basic compound (DA), compounds having structures represented by the following formulae (A) to (E) are preferred.

[0640] [Chemical formula 50]

[0641]

[0642] In the general formulae (A) and (E),

[0643] R 200 , R 201 and R 202 R may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). 201 With R 202 They may be bonded to each other to form a ring.

[0644] R 203 , R 204 , R 205 and R 206 The groups may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0645] The alkyl group in the general formula (A) and (E) may have a substituent or may be unsubstituted.

[0646] As for the 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 preferred.

[0647] More preferably, the alkyl groups in the general formulae (A) and (E) are unsubstituted.

[0648] As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine or piperidine are preferred, and compounds having an imidazole structure, a diazabicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or an aniline derivative having a hydroxyl group and / or an ether bond are more preferred.

[0649] The basic compound (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (DB)") is a compound having a proton accepting functional group and which decomposes by irradiation with actinic rays or radiation, thereby reducing or eliminating the proton accepting property or changing from proton accepting property to acidic property.

[0650] The proton accepting functional group refers to a group that can electrostatically interact with a proton or a functional group having an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to π conjugation. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation refers to, for example, a nitrogen atom having a partial structure shown in the following formula.

[0651] [Chemical formula 51]

[0652] Unshared electron pairs

[0653] Preferred partial structures of the proton accepting functional group include, for example, a crown ether structure, an azacrown ether structure, a primary amine structure to a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

[0654] Compound (DB) generates a compound whose proton accepting property decreases, disappears, or changes from proton accepting property to acidic property by decomposition under irradiation with actinic rays or radiation. Here, the decrease, disappearance, or change from proton accepting property to acidic property refers to the change of proton accepting property caused by the addition of proton to the proton accepting functional group, and specifically, it means that when a proton adduct is generated from the compound (DB) having a proton accepting functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.

[0655] The proton acceptor property can be confirmed by measuring pH.

[0656] The acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably -13<pKa<-1, and further preferably -13<pKa<-3.

[0657] The acid dissociation constant pKa refers to the acid dissociation constant pKa in an aqueous solution, for example, as defined by Chemistry Handbook (II) (revised 4th edition, 1993, compiled by the Chemical Society of Japan, Maruzen. Inc.). The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured using an infinite dilution aqueous solution, and can be measured by measuring the acid dissociation constant at 25°C. Alternatively, the following software package 1 can be used to calculate the value of a database based on Hammett's substituent constant and a known literature value. All pKa values ​​recorded in this specification represent the values ​​calculated using the software package.

[0658] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007ACD / Labs).

[0659] In the composition of the present invention, an onium salt (DC) that is a relatively weak acid with respect to the photoacid generator can be used as an acid diffusion controller.

[0660] When a photoacid generator and an onium salt that generates an acid that is relatively weak relative to the acid generated by the photoacid generator are used in combination, if the acid generated by the photoacid generator collides with the onium salt having unreacted weak acid anions by irradiation with actinic rays or radiation, the weak acid is released by salt exchange to generate an onium salt having strong acid anions. In this process, the strong acid is exchanged for a weak acid with lower catalytic performance, so the acid is apparently inactivated and the acid diffusion can be controlled.

[0661] As the onium salt that is a relatively weak acid with respect to the photoacid generator, compounds represented by the following general formulae (d1-1) to (d1-3) are preferred.

[0662] [Chemical formula 52]

[0663]

[0664] In the formula, R 51 represents a hydrocarbon group, Z 2c Represents a hydrocarbon group, R 52 represents an organic group, Y 3 represents an alkylene group, a cycloalkylene group or an arylene group, Rf represents a hydrocarbon group containing a fluorine atom, M + Each independently represents an ammonium cation, a sulfonium cation or an iodonium cation.

[0665] R 51 The represented hydrocarbon group may have a substituent.

[0666] Z 2c The hydrocarbon group represented preferably has 1 to 30 carbon atoms.

[0667] Z 2c The hydrocarbon group represented by may have a substituent. 2c In the hydrocarbon group represented by , it is preferred that the fluorine atom in the carbon atom adjacent to S is not substituted.

[0668] Y 3 When representing an alkylene group, it may be linear or branched.

[0669] As M + Preferred examples of the sulfonium cation or iodonium cation represented by include the sulfonium cation exemplified by the general formula (ZI) and the iodonium cation exemplified by the general formula (ZII).

[0670] The onium salt (DC) that is a relatively weak acid with respect to the photoacid generator may be a compound having a cation site and an anion site in the same molecule, wherein the cation site and the anion site are linked by a covalent bond (hereinafter also referred to as “compound (DCA)”).

[0671] As the compound (DCA), a compound represented by any one of the following general formulae (C-1) to (C-3) is preferred.

[0672] [Chemical formula 53]

[0673]

[0674] In the general formulas (C-1) to (C-3),

[0675] R1, R2 and R3 each independently represent a substituent having 1 or more carbon atoms.

[0676] L1 represents a divalent linking group or a single bond that links the cationic part and the anionic part.

[0677] -X - Indicates selected from -COO - 、-SO3 - 、-SO2 - and -N - -R4 anionic site. R4 represents a monovalent substituent having at least one of a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O)2-) and a sulfinyl group (-S(=O)-) at the site of connection with the adjacent N atom.

[0678] R1, R2, R3, R4 and L1 may be bonded to each other to form a ring structure. In the general formula (C-3), two of R1 to R3 taken together represent a divalent substituent group, which may be bonded to the N atom via a double bond.

[0679] Examples of the substituent having 1 or more carbon atoms in R1 to R3 include alkyl, cycloalkyl, aryl, alkoxycarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, and arylaminocarbonyl groups, and preferably alkyl, cycloalkyl, or aryl groups.

[0680] As the divalent linking group L1, there can be mentioned 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 carbamate bond, a urea bond, and a group formed by combining two or more of them. L1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of them.

[0681] The low molecular weight compound (DD) having a nitrogen atom and a group that is dissociated by the action of an acid (hereinafter also referred to as "compound (DD)") is preferably an amine derivative having a group that is dissociated by the action of an acid on the nitrogen atom.

[0682] The group that is released by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group or a hemiamalin ether group, and more preferably a carbamate group or a hemiamalin ether group.

[0683] The molecular weight of the compound (DD) is preferably 100 to 1,000, more preferably 100 to 700, and even more preferably 100 to 500.

[0684] 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).

[0685] [Chemical formula 54]

[0686]

[0687] In the general formula (d-1),

[0688] R b Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). b They may be bonded to each other to form a ring.

[0689] R b The alkyl, cycloalkyl, aryl and aralkyl groups represented by may be independently substituted by a hydroxyl, cyano, amino, pyrrolidinyl, piperidinyl, morpholinyl, oxo or other functional group, an alkoxy group or a halogen atom. b The same applies to the alkoxyalkyl groups represented.

[0690] As R b , preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group, more preferably a linear or branched alkyl group or a cycloalkyl group.

[0691] As two R b Examples of the ring formed by linking together include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.

[0692] Examples of specific structures of the group represented by the general formula (d-1) include structures disclosed in paragraph <0466> of US Patent Publication No. US2012 / 0135348A1, but the present invention is not limited thereto.

[0693] The compound (DD) preferably has a structure represented by the following general formula (6).

[0694] [Chemical formula 55]

[0695]

[0696] In general formula (6),

[0697] l represents an integer from 0 to 2, m represents an integer from 1 to 3, and l+m=3 is satisfied.

[0698] R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two R a Can be the same or different, 2 R a They may be linked to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.

[0699] R b and R in the above general formula (d-1) bThe meanings are the same, and preferred examples are also the same.

[0700] In the general formula (6), as R a The alkyl, cycloalkyl, aryl and aralkyl groups may be substituted independently by the following groups which are the same as the above groups: b The alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted.

[0701] As the above R a Specific examples of the alkyl, cycloalkyl, aryl and aralkyl groups (these groups may be substituted by the above groups) include the following: b The same groups as the above-mentioned specific examples.

[0702] Specific examples of particularly preferred compound (DD) in the present invention include compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012 / 0135348A1, but the present invention is not limited thereto.

[0703] The onium salt compound (DE) having a nitrogen atom in the cationic portion (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cationic portion. The basic site is preferably an amino group, more preferably an aliphatic amino group. All atoms adjacent to the nitrogen atom in the basic site are further preferably hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferred that the electron-withdrawing functional group (carbonyl, sulfonyl, cyano, halogen atom, etc.) is not directly bonded to the nitrogen atom.

[0704] Preferred specific examples of compound (DE) include compounds disclosed in paragraph <0203> of the specification of US Patent Application Publication No. 2015 / 0309408A1, but the present invention is not limited thereto.

[0705] Preferred examples of the acid diffusion controller are shown below.

[0706] [Chemical formula 56]

[0707]

[0708] [Chemical formula 57]

[0709]

[0710] In the composition of the present invention, the acid diffusion controller may be used alone or in combination of two or more.

[0711] The content of the acid diffusion controller in the composition of the present invention (the total when two or more types are present) is preferably 0.05 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content of the composition.

[0712] <Hydrophobic resin>

[0713] The composition of the present invention may contain a hydrophobic resin. In addition, the hydrophobic resin is preferably a resin different from the resin (A).

[0714] By containing a hydrophobic resin in the composition of the present invention, the static / dynamic contact angle on the surface of the actinic ray or radiation-sensitive film can be controlled, thereby improving the developing characteristics, suppressing outgassing, improving the immersion liquid followability during immersion exposure, and reducing immersion defects.

[0715] The hydrophobic resin is preferably designed to be localized on the surface of the resist film, but unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule and may not affect the uniform mixing of polar and non-polar substances.

[0716] From the viewpoint of being biased toward the surface layer of the film, the hydrophobic resin is preferably a resin containing at least one repeating unit selected from the group consisting of "fluorine atom", "silicon atom" and "CH3 partial structure contained in the side chain portion of the resin". When the hydrophobic resin contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chain.

[0717] When the hydrophobic resin contains a fluorine atom, it is preferably a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.

[0718] It is preferred that the hydrophobic resin has at least one group selected from the following group (x) to (z).

[0719] (x) Acid group

[0720] (y) a group that is decomposed by the action of an alkaline developer and whose solubility in the alkaline developer increases (hereinafter also referred to as a polarity conversion group)

[0721] (z) Groups that decompose by the action of an acid

[0722] Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (alkylsulfonyl) (alkylcarbonyl) imide group, a bis(alkylcarbonyl) methylene group, a bis(alkylcarbonyl) imide group, a bis(alkylsulfonyl) methylene group, a bis(alkylsulfonyl) imide group, a tri(alkylcarbonyl) methylene group, and a tri(alkylsulfonyl) methylene group. Preferred acid groups include a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonylimide group, or a bis(alkylcarbonyl) methylene group.

[0723] As the group (y) that decomposes by the action of the alkaline developer and increases its solubility relative to the alkaline developer, for example, a lactone group, a carboxylate group (-COO-), an anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylic acid thioester group (-COS-), a carbonate group (-OC(O)O-), a sulfate group (-OSO2O-) and a sulfonate group (-SO2O-), etc., preferably a lactone group or a carboxylate group (-COO-). As a repeating unit containing these groups, for example, a repeating unit in which these groups are directly bonded to the main chain of the resin, for example, a repeating unit based on acrylate and methacrylate can be mentioned. In the repeating unit, these groups can be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit is used when polymerizing a polymerization initiator or a chain transfer agent having these groups, and can be introduced into the end of the resin. Examples of the repeating unit having a lactone group include the same repeating units as those described above in the section of the resin (A) and having a lactone structure.

[0724] The content of the repeating unit having the group (y) which is decomposed by the action of an alkaline developer and has increased solubility in an alkaline developer is preferably 1 to 100 mol %, more preferably 3 to 98 mol %, and further preferably 5 to 95 mol % based on all the repeating units in the hydrophobic resin.

[0725] The repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin may include the same repeating unit as the repeating unit having an acid-decomposable group listed 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 a group (z) decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, and further preferably 20 to 60 mol% relative to all repeating units in the hydrophobic resin. The hydrophobic resin may further have a repeating unit different from the above-mentioned repeating unit.

[0726] The repeating unit containing fluorine atoms is preferably 10 to 100 mol %, more preferably 30 to 100 mol %, based on all repeating units in the hydrophobic resin. Furthermore, the repeating unit containing silicon atoms is preferably 10 to 100 mol %, more preferably 20 to 100 mol %, based on all repeating units in the hydrophobic resin.

[0727] On the other hand, particularly when the hydrophobic resin contains a CH3 partial structure in the side chain portion, it is also preferred that the hydrophobic resin substantially does not contain fluorine atoms and silicon atoms. In addition, it is preferred that the hydrophobic resin substantially consists of repeating units consisting only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

[0728] The weight average molecular weight of the hydrophobic resin in terms of standard polystyrene is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000.

[0729] The total content of residual monomers and / or oligomer components contained in the hydrophobic resin is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. The dispersion degree (Mw / Mn) is preferably in the range of 1 to 5, more preferably 1 to 3.

[0730] As the hydrophobic resin, known resins can be appropriately selected and used alone or in the form of a mixture thereof. For example, as the hydrophobic resin, known resins disclosed in sections <0451> to <0704> of U.S. Patent Application Publication No. 2015 / 0168830A1 and <0340> to <0356> of U.S. Patent Application Publication No. 2016 / 0274458A1 can be appropriately used. In addition, the repeating units disclosed in sections <0177> to <0258> of U.S. Patent Application Publication No. 2016 / 0237190A1 are also preferred as repeating units constituting the hydrophobic resin.

[0731] Preferred examples of monomers corresponding to the repeating units constituting the hydrophobic resin are shown below.

[0732] [Chemical formula 58]

[0733]

[0734] [Chemical formula 59]

[0735]

[0736] The hydrophobic resin may be used alone or in combination of two or more. From the viewpoint of taking into account both the immersion liquid followability and the developing characteristics during immersion exposure, it is preferred to use a mixture of two or more hydrophobic resins having different surface energies. 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, relative to the total solid content in the composition of the present invention.

[0737] <Solvent>

[0738] The composition of the present invention preferably contains a solvent. In the composition of the present invention, a known resist solvent can be appropriately used. For example, the known solvents disclosed in the paragraphs <0665> to <0670> of the specification of U.S. Patent Application Publication No. 2016 / 0070167A1, the paragraphs <0210> to <0235> of the specification of U.S. Patent Application Publication No. 2015 / 0004544A1, the paragraphs

[0424] to

[0426] of the specification of U.S. Patent Application Publication No. 2016 / 0237190A1, and the paragraphs

[0357] to

[0366] of the specification of U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used. Examples of the solvent that can be used when preparing the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

[0739] As an organic solvent, a mixed solvent of a solvent having a hydroxyl group in the structure and a solvent without a hydroxyl group can be used. As a solvent having a hydroxyl group and a solvent without a hydroxyl group, the aforementioned exemplary compounds can be preferably selected. As a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or lactic acid alkyl ester is preferred, and propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), 2-hydroxyisobutyric acid methyl ester or ethyl lactate is more preferred. In addition, as a solvent without a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, a monoketone compound that can have a ring, a cyclic lactone or an acetic acid alkyl is preferred. Among them, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone are further preferred. As a solvent without a hydroxyl group, propylene carbonate is also preferred. The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is 1 / 99 to 99 / 1, preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 60 / 40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent not having a hydroxyl group is preferred. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate, or may be a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

[0740] <Surfactant>

[0741] The composition of the present invention preferably contains a surfactant. When containing a surfactant, a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) is preferred.

[0742] The composition of the present invention contains a surfactant, and when using an exposure light source below 250nm, especially below 220nm, a pattern with good adhesion and few development defects can be obtained with good sensitivity and resolution. As fluorine-based and / or silicon-based surfactants, surfactants described in paragraph <0276> of the specification of U.S. Patent Application Publication No. 2008 / 0248425 can be cited. In addition, other surfactants other than fluorine-based and / or silicon-based surfactants described in paragraph <0280> of the specification of U.S. Patent Application Publication No. 2008 / 0248425 can also be used.

[0743] These surfactants can be used alone or in combination. When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, relative to the total solid content of the composition. On the other hand, by setting the content of the surfactant to 10 ppm (parts per million) or more relative to the total solid content of the composition, the surface localization of the hydrophobic resin is improved. As a result, the surface of the photosensitive or radiation-sensitive film can be made more hydrophobic, and the water tracking property during immersion exposure is improved.

[0744] <Resin(J)>

[0745] The composition of the present invention may contain 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 resin (J) may contain the aforementioned acid-decomposable group.

[0746] 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).

[0747] [Chemical formula 60]

[0748]

[0749] In the general formula (II),

[0750] R2 represents a hydrogen atom, an alkyl group which may have a substituent (preferably a methyl group), or a halogen atom (preferably a fluorine atom).

[0751] B' represents a single bond or a divalent linking group.

[0752] Ar' represents an aromatic ring group.

[0753] m represents an integer greater than 1. One type of resin (J) may be used alone, or two or more types may be used simultaneously. The content of resin (J) in the total solid content of the composition of the present invention is usually 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more. There is no particular restriction on the upper limit, but it is preferably 99% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. As resin (J), the resin disclosed in paragraphs <0142> to <0347> of the specification of U.S. Patent Application Publication No. 2016 / 0282720A1 can be preferably used.

[0754] (Other additives)

[0755] The composition of the present invention may further contain an acid multiplier, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor or a dissolution accelerator, etc. As the plasticizer, for example, polyalkylene glycol (the number of carbon atoms in the oxyalkylene unit is preferably 2 to 6, more preferably 2 to 3, and the average addition number is preferably 2 to 10, more preferably 2 to 6). As the plasticizer, specifically, for example, the following plasticizers can be mentioned.

[0756] [Chemical formula 61]

[0757]

[0758] 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.

[0759] <Preparation method>

[0760] The solid content concentration of the composition of the present invention is preferably 10% by mass or more, and its upper limit is usually preferably about 50% by mass. Among them, as the solid content concentration of the composition of the present invention, it is preferably 10 to 50% by mass, more preferably 25 to 50% by mass, and further preferably 30 to 50% by mass. The solid content concentration refers to the mass percentage of the mass of other resist components other than the solvent relative to the total mass of the composition.

[0761] In addition, the film thickness of the photosensitive ray or radiation-sensitive film (resist film) comprising the composition of the present invention is preferably 1 μm or more, and is preferably 3 μm or more, more preferably 5 μm or more, and further preferably 10 μm or more for the purpose of improving the injection resistance of increasing the number of processing stages. The upper limit is not particularly limited, for example, 100 μm or less. In addition, as described later, a pattern can be formed by the composition of the present invention. The film thickness of the formed pattern is preferably 1 μm or more, and is preferably 3 μm or more, more preferably 5 μm or more, and further preferably 10 μm or more for the purpose of improving the injection resistance of increasing the number of processing stages. The upper limit is not particularly limited, for example, 100 μm or less.

[0762] Regarding the composition of the present invention, the above-mentioned components are dissolved in a prescribed organic solvent, preferably dissolved in the above-mentioned mixed solvent, filtered by a filter, and then applied to a prescribed support (substrate) for use. The pore size of the filter used in the filter filtration is preferably less than 0.1 μm, more preferably less than 0.05 μm, and further preferably less than 0.03 μm. In addition, when the solid content concentration of the composition of the present invention is high (for example, more than 25% by mass), the pore size of the filter used in the filter filtration is preferably less than 3 μm, more preferably less than 0.5 μm, and further preferably less than 0.3 μm. The filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. Regarding the filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-062667 (Japanese Patent Application Publication No. 2002-062667), a circulation filtration can be performed, or a plurality of filters can be connected in series or in parallel for filtration. In addition, the composition can also be filtered multiple times. In addition, the composition can also be degassed before and after the filter filtration.

[0763] The viscosity of the composition of the present invention is preferably 100 to 500 mPa·s. From the viewpoint of better coating properties, the viscosity of the composition of the present invention is more preferably 100 to 300 mPa·s. The viscosity can be measured using an E-type viscometer.

[0764] <Application>

[0765] The composition of the present invention is an actinic ray or radiation-sensitive resin composition that reacts and changes its properties by irradiation with actinic rays or radiation. More specifically, the composition of the present invention is an actinic ray or radiation-sensitive resin composition used in a semiconductor manufacturing process such as an IC (Integrated Circuit), the manufacture of a circuit substrate such as a liquid crystal or a thermal head, the preparation of a mold structure for an imprint, and other photosensitive etching processes or the manufacture of a lithographic printing plate or an acid-curable composition. In the present invention, the formed pattern can be used in an etching process, an ion implantation process, a bump electrode formation process, a rewiring formation process, and MEMS (MicroElectro Mechanical Systems).

[0766] [Pattern forming method]

[0767] The present invention also relates to a pattern forming method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition. The pattern forming method of the present invention is described below. In addition, together with the description of the pattern forming method, the actinic ray-sensitive or radiation-sensitive film of the present invention is also described.

[0768] The pattern forming method of the present invention has the following steps:

[0769] (i) a step of forming a resist film (actinic ray-sensitive or radiation-sensitive film) on a support using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition (resist film forming step);

[0770] (ii) a step of exposing the resist film to light (irradiating it with actinic rays or radiation) (exposure step); and

[0771] (iii) A step of developing the exposed resist film using a developer (development step).

[0772] The pattern forming method of the present invention is not particularly limited as long as it includes the above-mentioned 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 liquid immersion exposure. In the pattern forming method of the present invention, it is preferred to include a (iv) preheating (PB: PreBake) step before the (ii) exposure step. In the pattern forming method of the present invention, it is preferred to include a (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 multiple (ii) exposure steps. In the pattern forming method of the present invention, multiple (iv) preheating steps may be included. In the pattern forming method of the present invention, multiple (v) post-exposure heating steps may be included.

[0773] In the pattern forming method of the present invention, the above-mentioned (i) resist film forming step, (ii) exposure step and (iii) development step can be carried out by a generally known method. In the pattern forming method of the present invention, (i) in the resist film forming step, the film thickness of the photosensitive ray or radiation-sensitive linear film formed on the substrate is preferably 1 μm or more, more preferably 3 μm or more, further preferably 5 μm or more, and particularly preferably 10 μm or more as described above. The upper limit is not particularly limited, for example, it is 100 μm or less. In addition, as needed, a resist lower film (for example, SOG (Spin On Glass: spin-coated glass), SOC (Spin On Carbon: spin-coated carbon) and an anti-reflective film) can be formed between the resist film and the support. As a material constituting the resist lower film, a known organic or inorganic material can be appropriately used. A protective film (top coat) can be formed on the upper layer of the resist film. As a protective film, a known material can be appropriately used. For example, the protective film forming composition disclosed in U.S. Patent Application Publication No. 2007 / 0178407, U.S. Patent Application Publication No. 2008 / 0085466, U.S. Patent Application Publication No. 2007 / 0275326, U.S. Patent Application Publication No. 2016 / 0299432, U.S. Patent Application Publication No. 2013 / 0244438, and International Patent Application Publication No. 2016 / 157988A can be preferably used. As the protective film forming composition, a composition containing the above-mentioned acid diffusion control agent is preferably used. A protective film can also be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.

[0774] The support is not particularly limited, and a substrate commonly used in a photolithography process of other photosensitive etching processes, in addition to a manufacturing process of semiconductors such as ICs or a manufacturing process of circuit substrates such as liquid crystals or thermal heads, can be used. Specific examples of the support include inorganic substrates such as silicon, SiO2, and SiN.

[0775] The heating temperature in either the preheating step (iv) or the post-exposure heating step (v) is preferably 70 to 150° C., more preferably 70 to 130° C., further preferably 80 to 130° C., and most preferably 80 to 120° C. The heating time in either the preheating step (iv) or the post-exposure heating step (v) is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds. Heating can be performed using a mechanism provided in the exposure device and the developing device, or using a heating plate or the like.

[0776] There is no limitation on the wavelength of the light source used in the exposure process, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among them, far ultraviolet light is preferred, and its wavelength is preferably 1 to 300 nm, more preferably 100 to 300 nm, and further preferably 200 to 300 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV (13 nm), and electron beams, and KrF excimer laser, ArF excimer laser, EUV, or electron beams are preferred, and KrF excimer laser is more preferred.

[0777] In the developing step (iii), an alkaline developer may be used, or a developer containing an organic solvent (hereinafter also referred to as an organic developer) may be used.

[0778] As an alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide is generally used. In addition, an alkaline aqueous solution such as an inorganic base, a primary amine to a tertiary amine, an alcohol amine, and a cyclic amine can also be used. In addition, the alkaline developer may contain an appropriate amount of alcohols and / or a surfactant. The alkali concentration of the alkaline developer is generally 0.1 to 20% by mass. The pH of the alkaline developer is generally 10 to 15. The time for developing using the alkaline developer is generally 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.

[0779] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0780] Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone and propylene carbonate.

[0781] Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate.

[0782] As the alcohol solvent, amide solvent, ether solvent, and hydrocarbon solvent, solvents disclosed in paragraphs <0715> to <0718> of the specification of US Patent Application Publication No. 2016 / 0070167A1 can be used.

[0783] The above solvents may be mixed in plurality, or may be mixed with solvents 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 particularly preferably 95 to 100% by mass relative to the total amount of the developer.

[0784] The organic developer may contain an appropriate amount of a known surfactant as necessary.

[0785] The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.

[0786] The organic developer may contain the above-mentioned acid diffusion controller.

[0787] As the developing method, for example, there can be cited: a method of immersing a substrate in a tank filled with a developer for a certain period of time (immersion method); a method of raising the developer on the surface of the substrate by surface tension and leaving it to stand for a certain period of time (immersion method); a method of spraying the developer on the surface of the substrate (spray method); or a method of continuously spraying the developer at a certain speed while scanning the developer spray nozzle on a substrate rotating at a certain speed (dynamic distribution method), etc.

[0788] The process of developing with an alkaline aqueous solution (alkaline developing process) and the process of developing with a developer containing an organic solvent (organic solvent developing process) may be combined. Thus, only the region with the intermediate exposure intensity is insoluble to form a pattern, thereby forming a finer pattern.

[0789] After the (iii) development step, it is preferable to include a step of washing with a washing liquid (rinsing step).

[0790] The rinse liquid used in the rinse process after the development process using an alkaline developer can be, for example, pure water. The pure water may contain an appropriate amount of surfactant. In this case, after the development process or the rinse process, a treatment of removing the developer or rinse liquid attached to the pattern by a supercritical fluid may be performed. Furthermore, after the rinse process or the treatment based on the supercritical fluid, a heat treatment may be performed to remove the water remaining in the pattern.

[0791] The rinse solution used in the rinse process after the development process using a developer containing an organic solvent is not particularly limited as long as it is a rinse solution that does not dissolve the pattern, and a solution containing a general organic solvent can be used. As the rinse solution, it is preferred to use a rinse solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. As specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, the same solvents as those described in the developer containing an organic solvent can be cited. As the rinse solution used in the rinse process at this time, a rinse solution containing a monohydric alcohol is more preferred.

[0792] As the monohydric alcohol used in the rinsing step, linear, branched or cyclic monohydric alcohols can be mentioned. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-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-hexanol, 3-octanol, 4-octanol and methyl isobutyl carbinol can be mentioned. As the monohydric alcohol having 5 or more carbon atoms, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and methyl isobutyl carbinol can be mentioned.

[0793] Each component can be mixed in multiples, or can be mixed with an organic solvent other than the above. The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

[0794] The rinse solution may contain a suitable amount of a surfactant. In the rinse step, a rinse solution containing an organic solvent is used to rinse the substrate that has been developed using an organic developer. The method of the rinse treatment is not particularly limited, and examples thereof include: a method of continuously spraying a rinse solution on a substrate that is rotating at a certain speed (spin coating); a method of immersing a substrate in a tank filled with a rinse solution for a certain period of time (immersion); or a method of spraying a rinse solution onto the surface of a substrate (spraying). Among them, it is preferred to perform the rinse treatment using a spin coating method, and after the rinse, the substrate is rotated at a speed of 2,000 to 4,000 rpm (revolution per minute) to remove the rinse solution from the substrate. In addition, it is also preferred to include a heating step (Post Bake) after the rinse step. The developer and rinse solution remaining between and inside the patterns are removed by this heating step. In the heating step after the rinsing step, the heating temperature is usually 40 to 160° C., preferably 70 to 120° C., more preferably 70 to 95° C., and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

[0795] The various materials used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention (e.g., resist solvent, developer, rinse solution, antireflection film forming composition or topcoat layer forming composition, etc.) preferably do not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt (parts pertrillion: parts per trillion) or less, further preferably 10 ppt or less, and particularly preferably substantially free (below the detection limit of the measuring device).

[0796] As a method for removing impurities such as metals from the above-mentioned various materials, for example, filtration using a filter can be cited. As the filter pore size, the pore size is preferably less than 10nm, more preferably less than 5nm, and further preferably less than 3nm. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferred. The filter can also use a filter pre-cleaned with an organic solvent. In the filter filtering process, a variety of filters can be connected in series or in parallel for use. When using a variety of filters, filters with different pore sizes and / or materials can also be used in combination. In addition, various materials can be filtered multiple times, and the process of filtering multiple times can also be a circulating filtration process. As a filter, a filter with reduced dissolution as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Publication No. 2016-201426) is preferred. In addition to filter filtration, impurities can also be removed using an adsorbent, and filter filtration and adsorbent can also be combined for use. As an adsorbent, a known adsorbent can be used, for example, an inorganic adsorbent such as silica gel or zeolite or an organic adsorbent such as activated carbon can be used. As metal adsorbents, for example, adsorbents disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Application Publication No. 2016-206500) can be cited. In addition, as methods for reducing impurities such as metals contained in the above-mentioned various materials, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting various materials, filtering the raw materials constituting various materials, or lining the device with TEFLON (registered trademark) to perform distillation under conditions that minimize contamination. The preferred conditions for filtering the raw materials constituting various materials are the same as the above conditions.

[0797] In order to prevent the mixing of impurities, the above-mentioned various materials are preferably stored in containers described in U.S. Patent Application Publication No. 2015 / 0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Laid-Open No. 2015-123351), and the like.

[0798] For the pattern formed by the pattern forming method of the present invention, a method for improving the surface roughness of the pattern can also be applied. As a method for improving the surface roughness of the pattern, for example, the method of treating the pattern using a plasma containing a hydrogen gas disclosed in U.S. Patent Application Publication No. 2015 / 0104957 can be cited. In addition, the known methods described in Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application No. 2004-235468), U.S. Patent Application Publication No. 2010 / 0020297, and Proc. of SPIE Vol. 8328 83280N-1 "EUV ResistCuring Technique for LWR Reduction and Etch Selectivity Enhancement" can also be applied. Furthermore, the pattern formed by the above method can be used as a core material of the 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 / 0209941.

[0799] [Method for manufacturing electronic device]

[0800] Furthermore, 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 can be appropriately mounted on electrical and electronic devices (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, and communication equipment, etc.).

[0801] Example

[0802] Below, the present invention is further described in detail based on examples. The materials, usage, ratio, processing content and processing steps shown in the following examples can be appropriately changed as long as they do not depart from the main purpose of the present invention. Therefore, the scope of the present invention is not to be interpreted restrictively by the examples shown below.

[0803] <Resin>

[0804] The structure of the repeating unit and its content (molar ratio), weight average molecular weight (Mw) and dispersion (Mw / Mn) of the resin used are shown. In addition, the weight average molecular weight (Mw) and dispersion (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene conversion). In addition, the content of the repeating unit is measured by 13The results were measured using C-NMR (nuclear magnetic resonance).

[0805] [Chemical formula 62]

[0806]

[0807] [Chemical formula 63]

[0808]

[0809] [Chemical formula 64]

[0810]

[0811] [Chemical formula 65]

[0812]

[0813] For each resin, the content (mol %) of the repeating unit (a1) derived from a monomer (monomer a1) having a glass transition temperature of 50° C. or less when used as a homopolymer, the type of monomer a1, the glass transition temperature (Tg) when monomer a1 is used as a homopolymer, the type of monomer corresponding to the repeating unit (a2) having an acid-decomposable group, the content of the repeating unit (a2), the type of monomer corresponding to the repeating unit (a3) ​​having a carboxyl group, the content of the repeating unit (a3), the type of monomer corresponding to the repeating unit (a4) having a phenolic hydroxyl group, the content of the repeating unit (a4), the type of monomer corresponding to other repeating units, and the content of other repeating units are described in Table 1. The content of each repeating unit is a molar ratio relative to all repeating units contained in the resin.

[0814] (Method for measuring glass transition temperature of homopolymer)

[0815] When there is a catalog value or a literature value, the glass transition temperature of the homopolymer is adopted. When there is no value, it is measured by differential scanning calorimetry (DSC). The weight average molecular weight (Mw) of the homopolymer used for Tg measurement is set to 18,000, and the dispersion (Mw / Mn) is set to 1.7. The thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Inc. was used as a DSC device, and the measurement was performed at a heating rate of 10°C / min. In addition, the homopolymer used for Tg measurement was synthesized by the following steps using the corresponding monomer. In addition, the synthesis of the homopolymer was carried out by the usual dropwise polymerization method. 54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was heated to 80°C under a nitrogen flow. While stirring the solution, 125 parts by mass of a PGMEA solution containing 21% by mass of the corresponding monomer and 0.35% by mass of 2,2'-dimethyl azobisisobutyrate was added dropwise over 6 hours. After the addition was completed, the mixture was further stirred at 80°C for 2 hours. After the reaction solution was cooled, it was precipitated again with a large amount of methanol / water (mass ratio 9:1), filtered, and the obtained solid was dried to obtain a homopolymer (Mw: 18000, Mw / Mn: 1.7). The obtained homopolymer was used for DSC measurement. The DSC device and heating rate were as described above.

[0816] [Table 1]

[0817]

[0818] In addition, the glass transition temperature of the monomer (ME-1) corresponding to the other repeating units contained in the resins AX-1 and AX-2 when it was made into a homopolymer was 54 degreeC.

[0819] [Chemical formula 66]

[0820]

[0821] [Chemical formula 67]

[0822]

[0823] <Acid generator>

[0824] The structures of the photoacid generators used are shown below.

[0825] [Chemical formula 68]

[0826]

[0827] [Chemical formula 69]

[0828]

[0829] [Chemical formula 70]

[0830]

[0831] [Chemical formula 71]

[0832]

[0833] <Acid Diffusion Controller> The acid diffusion controller used is shown below.

[0834] [Chemical formula 72]

[0835]

[0836] <Surfactant>

[0837] The surfactants used are shown below.

[0838] [Chemical formula 73]

[0839]

[0840] (E-2): MEGAFACE R-41 (manufactured by DIC Corporation)

[0841] <Other additives>

[0842] Other additives used are shown below.

[0843] [Chemical formula 74]

[0844]

[0845] [Chemical formula 75]

[0846]

[0847] <Solvent>

[0848] The solvents used are shown below.

[0849] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0850] S-2: Propylene glycol monomethyl ether (PGME)

[0851] S-3: Ethyl lactate (EL)

[0852] S-4: Ethyl 3-ethoxypropionate (EEP)

[0853] S-5: 2-Heptanone (MAK)

[0854] S-6: 3-methoxymethyl propionate (MMP)

[0855] S-7: 3-Methoxybutyl acetate

[0856] <Preparation of actinic ray-sensitive or radiation-sensitive resin composition>

[0857] The components shown in Table 2 were mixed to obtain a solution in a manner to obtain the solid content concentration (mass %) described in Table 2. Next, the obtained solution was filtered with a polyethylene filter having a pore size of 3 μm to prepare actinic ray-sensitive or radiation-sensitive resin compositions (resist compositions) res-1 to res-21, res-1X to res-4X. In addition, in the resist composition, the solid content refers to all components except the solvent.

[0858] In Table 2, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid content. In addition, Table 2 describes the content ratio (mass %) of the used solvent relative to the total solvent.

[0859] [Table 2]

[0860]

[0861] 〔Pattern formation and various evaluations〕

[0862] <Pattern formation>

[0863] Utilize the spin coater ACT-8 manufactured by Tokyo Electron Limited, on the Si substrate (Advanced Materials Technology company manufacture) implemented hexamethyldisilazane process, anti-reflection layer is not set and the resist composition prepared in the above-mentioned is dripped under the state that substrate is static.After dripping, rotate the substrate, its rotation speed is maintained for 3 seconds with 500rpm, then maintains 2 seconds with 100rpm, and then maintains 3 seconds with 500rpm, maintains 2 seconds with 100rpm again, increases to the film thickness setting rotation speed (1200rpm) and maintains 60 seconds.Then, carry out heating and drying for 60 seconds at 130 ℃ on a hot plate, thereby form the positive resist film of film thickness 11μm. The resist film was subjected to pattern exposure, and the pattern exposure was performed through a mask having a line-and-space pattern with a spatial width of 5 μm and a spacing width of 25 μm formed after reduced projection exposure and development, using a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C wavelength 248 nm) under exposure conditions of NA=0.60, σ=0.75. After irradiation, it was baked at 120°C for 60 seconds, immersed in a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with pure water for 30 seconds and dried, thereby forming an isolated space pattern with a spatial width of 5 μm and a spacing width of 25 μm. The above-mentioned pattern exposure is exposure through a mask having a line-and-space pattern with a spatial width of 5 μm and a spacing width of 25 μm after reduced projection exposure, and the exposure amount is set to the most preferred exposure amount (sensitivity) (mJ / cm 2 In determining the sensitivity, a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the spatial width of the pattern. Through the above steps, a pattern was formed on the substrate.

[0864] <Performance Evaluation>

[0865] Utilize the spin coater ACT-8 manufactured by Tokyo Electron Limited, on the Si substrate (Advanced Materials Technology company manufacture) implemented hexamethyldisilazane process, anti-reflection layer is not set and the resist composition prepared in the above-mentioned is dripped under the state that substrate is static.After dripping, rotate the substrate, its rotation speed is maintained for 3 seconds with 500rpm, then maintains 2 seconds with 100rpm, and then maintains 3 seconds with 500rpm, maintains 2 seconds with 100rpm again, increases to the film thickness setting rotation speed (1200rpm) and maintains 60 seconds.Then, carry out heating and drying for 60 seconds at 130 ℃ on a hot plate, thereby form the positive resist film of film thickness 11μm. The substrate (wafer) with the resist film was placed in a dry etching device (manufactured by Hitachi High-Technologies Corporation., U-621), and the etching process was continued for 30 seconds using a mixed gas of CF4, Ar, and N2 (gas ratio of 1:10:10) with a gas pressure of 4Pa, a plasma power of 1600W, and a substrate bias of 1200W, and the etching process was repeated 6 times using a mixed gas of O2 and CF4 (gas ratio of 20:1) with a gas pressure of 2Pa, a plasma power of 800W, and a substrate bias of 0W. The wafer after the etching process was disconnected, and the resist cross section was observed at a magnification of 10000 using a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Corporation., S-4800). The number of pores (voids) in the observed resist film was counted, and large pores (pores with a size of 50 nm or more) and small pores (pores with a size of less than 50 nm) were determined based on the following criteria.

[0866] [Number of macropores]

[0867] A: 0 (none observed)

[0868] B: Less than 10

[0869] C: 10 or more

[0870] [Number of small pores]

[0871] X: 0 (none observed)

[0872] Y: Less than 10

[0873] Z: 10 or more

[0874] [Table 3]

[0875] Number of macropores Number of small pores Example 1 A X Example 2 A Y Example 3 A Y Example 4 A X Example 5 A X Example 6 A X Example 7 A Y Example 8 A X Example 9 A Y Example 10 A Y Embodiment 11 A X Example 12 A Y Example 13 A X Embodiment 14 A X Embodiment 15 A X Example 16 A X Embodiment 17 A X Embodiment 18 A X Embodiment 19 A X Embodiment 20 A X Embodiment 21 A Y Comparative Example 1 A Z Comparative Example 2 C Z Comparative Example 3 B Y Comparative Example 4 B Z

[0876] As can be seen from the results of Table 3, the resist composition of the embodiment suppresses the generation of macropores in the resist film and also reduces small pores. In particular, in the embodiment, extremely small pores less than 20 nm in size are not observed at all or even if observed, there are less than 10. Therefore, according to the resist composition of the embodiment, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern in which macropores and small pores are not easily generated inside the pattern during etching, a resist film formed by the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A) and a compound that generates an acid upon irradiation with actinic rays or radiation, In the actinic ray-sensitive or radiation-sensitive resin composition, the content of the resin (A) is 40% by mass or more based on the total solid content. The resin (A) comprises a repeating unit a1 derived from a monomer having a glass transition temperature of 50° C. or less when formed as a homopolymer and a repeating unit a2 having an acid-decomposable group, The repeating unit a1 is a non-acid decomposable repeating unit, The resin (A) contains, as the repeating unit (a1), one or more of a repeating unit represented by the following general formula (1-2) or a repeating unit represented by the following general formula (1-3), In the resin (A), the content of the repeating unit (a1) is 5 mol% to 50 mol% relative to all the repeating units of the resin (A). The compound that generates an acid upon irradiation with the actinic ray or radiation includes a compound represented by the following general formula (P-1): In the general formula (1-2), R1 represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group, and R2 represents a non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain; In the general formula (1-3), R3 represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group, and R4 represents a non-acid-decomposable alkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the ring element. In the above general formula (P-1), Q1 means including S + The ring, Ring Q1 is a 4-membered ring, a 5-membered ring or a 6-membered ring, wherein Ring Q1 may form a condensed ring with other rings. Ring Q1 has at least 2 carbon atoms as ring elements, and S + The atoms of the ring elements directly bonded are carbon atoms, R P1 ~R P5 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group, and R P1 ~R P5 At least two of them are optionally bonded to form a ring, Z - Represents a non-nucleophilic anion.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein The Q1 is a non-aromatic ring.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The Q1, as a ring element, has S + Other heteroatoms.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The compound represented by the general formula (P-1) is a compound represented by the following general formula (P-2), In the above general formula (P-2), R P1 ~R P5 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group, and R P1 ~R P5 At least two of them are optionally bonded to form a ring, R P6 ~R P9 each independently represents a hydrogen atom or a substituent, m1 and m2 each independently represent 1 or 2, R P6 ~R P9 When there are multiple, they can be the same or different. When m1 represents 2, 2 R P6 are optionally bonded to each other to form a ring, When m2 represents 2, 2 R P8 are optionally bonded to each other to form a ring, M1 represents a heteroatom or -CR P10 R P11 -, R P10 and R P11 each independently represents a hydrogen atom or a substituent, Z - Represents a non-nucleophilic anion.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The compound represented by the general formula (P-1) is a compound represented by the following general formula (P-3), In the above general formula (P-3), R P1 , R P2 , R P4 and R P5 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group, R P6 ~R P9 each independently represents a hydrogen atom or a substituent, m1 and m2 each independently represent 1 or 2, R P6 ~R P9 When there are multiple, they can be the same or different. When m1 represents 2, 2 R P6 are optionally bonded to each other to form a ring, When m2 represents 2, 2 R P8 are optionally bonded to each other to form a ring, M1 represents a heteroatom or -CR P10 R P11 -, R P10 and R P11 each independently represents a hydrogen atom or a substituent, R P12 represents a hydrogen atom or an alkyl group, R P1 , R P2 , R P4 , R P5 and R P12 At least two of them are optionally bonded to form a ring, Z - Represents a non-nucleophilic anion.

6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The compound represented by the general formula (P-1) is a compound represented by the following general formula (P-4) or (P-5), In the above general formulas (P-4) and (P-5), R P1 , R P2 , R P4 and R P5 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group, R P6 ~R P9 each independently represents a hydrogen atom or a substituent, There are multiple R P6 ~R P9 They can be the same or different. 2 R's P6 are optionally bonded to each other to form a ring, 2 R's P8 are optionally bonded to each other to form a ring, M1 represents a heteroatom or -CR P10 R P11 -, R P10 and R P11 each independently represents a hydrogen atom or a substituent, R P12 represents a hydrogen atom or an alkyl group, R P1 , R P2 , R P4 , R P5 and R P12 At least two of them are optionally bonded to form a ring, Z - represents a non-nucleophilic anion, In the above general formula (P-5), R P13 represents a hydrogen atom or a substituent.

7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is 10% by mass or more.

8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The Z - is an anion represented by any one of the following general formulas (Z1) to (Z4), In the general formula (Z1), R Z1 represents an alkyl group, In the general formula (Z2), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and a plurality of Xf each may be the same or different. R Z2 and R Z3 Each independently represents a hydrogen atom, a fluorine atom or an alkyl group. When there are multiple R Z2 and R Z3 They can be the same or different. L Z1 represents a divalent linking group, and when there are multiple L Z1 Optional same or different, A Z1 represents an organic group containing a cyclic structure, x represents an integer from 1 to 20, y represents an integer from 0 to 10, z represents an integer from 0 to 10, In general formulae (Z3) and (Z4), Rb3 to Rb7 each independently represent an alkyl group, a cycloalkyl group or an aryl group, Rb3 and Rb4 may be bonded to form a ring structure, and Rb5 and Rb6 may be bonded to form a ring structure.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The resin (A) contains a repeating unit having an aromatic ring. 10 . A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 .

11. A pattern forming method, comprising: (i) forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 1 μm or more on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition; (ii) irradiating the actinic ray or radiation sensitive film with actinic rays or radiation having a wavelength of 200 nm to 300 nm; and (iii) a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation with a developer, The actinic ray-sensitive or radiation-sensitive resin composition contains a resin (A) and a compound that generates an acid upon irradiation with actinic rays or radiation. In the actinic ray-sensitive or radiation-sensitive resin composition, the content of the resin (A) is 40% by mass or more based on the total solid content. The resin (A) comprises a repeating unit (a1) derived from a monomer having a glass transition temperature of 50° C. or less when formed as a homopolymer and a repeating unit (a2) having an acid-decomposable group, The repeating unit (a1) is a non-acid-decomposable repeating unit, The resin (A) contains, as the repeating unit (a1), one or more of a repeating unit represented by the following general formula (1-2) or a repeating unit represented by the following general formula (1-3), In the resin (A), the content of the repeating unit (a1) is 5 mol% to 50 mol% relative to all the repeating units of the resin (A). The compound that generates an acid upon irradiation with the actinic ray or radiation includes a compound represented by the following general formula (P-1): In the general formula (1-2), R1 represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group, and R2 represents a non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain; In the general formula (1-3), R3 represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group, and R4 represents a non-acid-decomposable alkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group which may contain a heteroatom in the ring element. In the above general formula (P-1), Q1 means including S + The ring, Ring Q1 is a 4-membered ring, a 5-membered ring or a 6-membered ring, wherein Ring Q1 optionally forms a condensed ring with other rings, Ring Q1 has at least 2 carbon atoms as ring elements, and S + The atoms of the ring elements directly bonded are carbon atoms, R P1 ~R P5 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an alkoxy group, and R P1 ~R P5 At least two of them are optionally bonded to form a ring, Z - Represents a non-nucleophilic anion. 12 . A method for manufacturing an electronic device, comprising the pattern forming method according to claim 11 .

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