Radiation-sensitive or radio-sensitive resin composition, radiation-sensitive or radio-sensitive film, method for forming a pattern, and method for manufacturing an electronic device

Abstract

The present invention provides a photosensitive actinic ray- or radiation-sensitive resin composition, a photosensitive actinic ray- or radiation-sensitive film formed from the photosensitive actinic ray- or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device. The photosensitive actinic ray- or radiation-sensitive resin composition contains (A) a resin and (B) a compound represented by a specific general formula (1) that generates an acid upon irradiation with actinic rays or radiation.

Description

Technical Field

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

[0002] After the KrF excimer laser (248 nm) resist, in order to compensate for the reduction in sensitivity caused by light absorption, a pattern forming method using chemical amplification has been used. For example, in the positive chemical amplification method, first, a photoacid generator contained in the exposed portion decomposes by light irradiation to generate an acid. Then, in the post-exposure bake (PEB) process or the like after exposure, the acid-catalyzed action of the generated acid changes the base-insoluble group contained in the photosensitive composition into a base-soluble group. Then, for example, development is performed using an alkaline solution. Thereby, the exposed portion is removed to obtain a desired pattern.

[0003] In the above method, various alkaline developers have been proposed as the alkaline developer. For example, as the alkaline developer, an aqueous alkaline developer of 2.38 mass% TMAH (aqueous solution of tetramethylammonium hydroxide) is usually used.

[0004] For the miniaturization of semiconductor elements, the shortening of the exposure light source wavelength and the increase in the numerical aperture (high NA) of the projection lens have been continuously progressing, and an exposure apparatus using an ArF excimer laser having a wavelength of 193 nm as a light source is now being developed. As a technique for further improving the resolution, a method of filling a liquid having a high refractive index (hereinafter, also referred to as "immersion liquid") between the projection lens and the specimen (i.e., immersion method) can be cited.

[0005] As a conventional resist composition, a multiple composition is known. However, for example, in Patent Document 1, a photosensitive radiation-curable or radiation-sensitive resin composition containing a compound that generates an acid by irradiation with actinic rays or radiation represented by a specific general formula and a resin is described.

[0006] Moreover, in Patent Document 2, a positive resist material is described, which includes a photoacid generator of a compound represented by a specific general formula and a base resin in which a hydrogen atom of a carboxyl group or a hydrogen atom of a phenolic hydroxyl group is substituted with an acid-labile group having a base dissolution control ability and the acid-labile group is dissociated by the action of an acid generated by exposure to increase the solubility in an alkaline aqueous solution.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2014-6491

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 2003-321466 Summary of the Invention

[0011] Technical Problem to be Solved by the Invention

[0012] However, a resist composition is usually stored for a specified period in a storage state. However, the performance of the resist composition has a tendency to deteriorate due to such storage over time. Therefore, a resist composition capable of achieving more excellent stability over time is required. (Here, excellent stability over time means that when the resist composition before forming a resist film is stored over time, the influence on the pattern obtained by using the composition after storage over time is small).

[0013] As a countermeasure, it is considered to change the composition of the resist composition to a composition that can improve the stability over time. However, it is actually not easy to find a composition that can further improve the stability over time.

[0014] Therefore, an object of the present invention is to provide a photosensitive or radiation-sensitive resin composition capable of achieving extremely excellent stability over time.

[0015] Another object of the present invention is to provide a photosensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned photosensitive or radiation-sensitive resin composition.

[0016] Means for Solving the Technical Problem

[0017] Now, as a result of the present inventors' in-depth study of the structure of a sulfonium salt compound as a compound (photoacid generator) that generates an acid by irradiation with actinic rays or radiation, a structure in which a sulfonium ring having a heteroatom as a ring member or its vicinity is shielded by a substituent and the arrangement position of the substituent is precisely controlled is formed. Although the detailed reason is not clear, surprisingly, it has been found that the stability over time is very excellent, and thus the present invention has been completed.

[0018] That is, the present invention has the following structure, thereby solving the above-mentioned problems of the present invention. [1]

[0020] A photosensitive or radiation-sensitive resin composition, comprising:

[0021] (A) a resin; and

[0022] (B) a compound represented by the following general formula (1) that generates an acid by irradiation with actinic rays or radiation.

[0023] [Chemical Formula 1]

[0024]

[0025] In general formula (1),

[0026] W1 represents a ring.

[0027] Q represents a divalent linking group in which one or more ring members constituting the ring W1 are heteroatoms, carbonyl carbon atoms, or a combination thereof.

[0028] R 1A and R 1B each independently represent a hydrogen atom, an organic group, a halogen atom, or a cyano group. Among them, at least one of R 1A and R 1B represents an organic group, a halogen atom, or a cyano group.

[0029] R 2A and R 2B each independently represent a hydrogen atom, an organic group, a halogen atom, or a cyano group. Among them, at least one of R 2A and R 2B represents an organic group, a halogen atom, or a cyano group.

[0030] p represents 0 or 1, and q represents 0 or 1.

[0031] Among them, p + q represents 1 or 2.

[0032] R1 and R2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. Among them, at least one of R1 and R2 represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0033] n represents 0 or 1.

[0034] R3 and R4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0035] m represents an integer of 0 or 1 or more.

[0036] When m represents an integer of 1 or more, n represents 1.

[0037] L represents a carbonyl bond or an ester bond.

[0038] l represents 0 or 1.

[0039] When l represents 1, n represents 1.

[0040] When l represents 1, at least two of R5 to R9 can be connected to each other to form a ring.

[0041] When l represents 0, m represents 0 and n represents 0.

[0042] R5, R6, R7, R8 and R9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or a cycloalkylthio group.

[0043] Z- represents an anion. [2]

[0045] The photosensitive or radiation-sensitive resin composition according to [1], wherein

[0046] In the above general formula (1), ring W1 is a 6- to 8-membered ring. [3]

[0048] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein, in the general formula (1), Z- is an anion represented by any one of the following general formulas (3) to (5).

[0049] [Chemical formula 2]

[0050]

[0051] In the general formula (3),

[0052] Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

[0053] L1 represents a single bond or a divalent linking group. A represents a monovalent organic group.

[0054] x represents an integer from 1 to 20.

[0055] [Chemical formula 3]

[0056]

[0057] In the general formula (4),

[0058] Xf1 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Two Xf1s may be connected to each other to form a ring structure.

[0059] [Chemical formula 4]

[0060]

[0061] In the general formula (5),

[0062] Xf2 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Two Xf2s may be connected to each other to form a ring structure. [4]

[0064] The photosensitive actinic or radiation-sensitive resin composition according to any one of [1] to [3], wherein,

[0065] In the general formula (1), Q is any linking group selected from the following group.

[0066] [Chemical formula 5]

[0067]

[0068] In the above formula,

[0069] R 11 represents a hydrogen atom or a substituent.

[0070] * represents a bonding site of a group adjacent to Q that forms W1 in the general formula (1). [5]

[0072] The photosensitive actinic or radiation-sensitive resin composition according to any one of [1] to [4], wherein,

[0073] The compound represented by the above general formula (1) is a compound represented by the following general formula (2).

[0074] [Chemical formula 6]

[0075]

[0076] In the general formula (2),

[0077] Ra to Rd each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0078] Among them, at least one of Ra to Rd represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0079] The meaning of Q is the same as the meaning of Q in the above general formula (1).

[0080] The meanings of R1 and R2 are the same as the meanings of R1 and R2 in the above general formula (1).

[0081] The meanings of R5, R6, R7, R8, and R9 are the same as the meanings of R5, R6, R7, R8, and R9 in the above general formula (1).

[0082] At least two of R5 to R9 may be connected to each other to form a ring.

[0083] The meaning of Z- is the same as the meaning of Z- in the above general formula (1). [6]

[0085] The photosensitive actinic or radiation-sensitive resin composition according to any one of [1] to [5], wherein,

[0086] In the above general formula (1) or general formula (2), at least one of R5 to R9 represents an alkoxy group, a cycloalkoxy group, an alkylthio group or a cycloalkylthio group. [7]

[0088] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein

[0089] The solid content concentration of the above composition is 10% by mass or more. [8]

[0091] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein

[0092] The above resin (A) has phenolic hydroxyl groups. [9]

[0094] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein

[0095] The above resin (A) has carboxyl groups.

[10]

[0097] A photosensitive or radiation-sensitive film formed from the photosensitive or radiation-sensitive resin composition according to any one of [1] to [9].

[11]

[0099] A pattern forming method, comprising:

[0100] An exposure step of exposing the photosensitive or radiation-sensitive film described in

[10] ; and

[0101] A development step of developing the exposed photosensitive or radiation-sensitive film using a developer.

[12]

[0103] A method for manufacturing an electronic device, comprising the pattern forming method described in

[11] .

[0104] Advantages of the Invention

[0105] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition capable of achieving extremely excellent stability over time.

[0106] According to the present invention, it is further possible to provide a photosensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the above photosensitive or radiation-sensitive resin composition. Detailed Description

[0107] Hereinafter, the content of the present invention will be described in detail.

[0108] The description of the constituent elements described below is based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0109] In the description of groups (atomic groups) in this specification, the notations of unsubstituted and substituted groups include not only groups without substituents but also groups with substituents. For example, "alkyl" includes not only alkyl without substituents (unsubstituted alkyl) but also alkyl with substituents (substituted alkyl). And, "organic group" in this specification means a group containing at least one carbon atom.

[0110] Moreover, in this specification, the type, position, and number of substituents when "may have substituents" are not particularly limited. The number of substituents can be, for example, 1, 2, 3, or more. As examples of substituents, monovalent non-metal atomic groups other than hydrogen atoms can be cited, and they can be selected from the following substituents T, for example.

[0111] (Substituent T)

[0112] As substituent T, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom can be cited; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxyacetyl group; alkylthio groups such as methylthio group and tert-butylthio group; arylthio groups such as phenylthio group and p-tolylthio group; alkyl; cycloalkyl; aryl; heteroaryl; hydroxyl group; carboxyl group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; formyl group; and combinations thereof.

[0113] "Actinic ray" or "radiation" in this specification means, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultrayiolet), X-rays, and electron beams (EB: Electron Beam). "Light" in this specification means actinic ray or radiation unless otherwise specified.

[0114] Unless otherwise specified, "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, EUV light, etc., but also exposure using particle rays such as electron beams and ion beams.

[0115] In this specification, "~" is used to indicate the meaning of including the numerical values described before and after it as the lower limit value and the upper limit value.

[0116] In this specification, (meth)acrylate represents acrylate and methacrylate, and (meth)acrylic acid represents acrylic acid and methacrylic acid.

[0117] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of the resin component are defined as the polystyrene conversion values obtained by GPC measurement using a GPC apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 °C, flow rate: 1.0 mL / minute, detector: refractive index detector).

[0118] In this specification, when there are multiple substances corresponding to each component in the composition, unless otherwise specified, the amount of each component in the composition refers to the total amount of the corresponding multiple substances present in the composition.

[0119] In this specification, the term "process" includes not only independent processes, but also cases where it cannot be clearly distinguished from other processes, as long as the intended purpose of the process can be achieved.

[0120] In this specification, "total solid content" refers to the total mass of the components obtained by removing the solvent from all the components of the composition. And, as described above, "solid content" refers to the components obtained by removing the solvent, which can be solid or liquid at 25 °C, for example.

[0121] In this specification, "mass %" has the same meaning as "weight %", and "parts by mass" has the same meaning as "parts by weight".

[0122] Moreover, in this specification, the combination of two or more preferred modes is a more preferred mode.

[0123] (Radiation-sensitive or radio-sensitive resin composition)

[0124] The radiation-sensitive or radio-sensitive resin composition (hereinafter also simply referred to as "composition") according to the present invention contains:

[0125] (A) A resin; and

[0126] (B) A compound represented by the following general formula (1) that generates an acid upon irradiation with actinic rays or radiation.

[0127] [Chemical formula 7]

[0128]

[0129] In general formula (1),

[0130] W1 represents a ring.

[0131] Q represents a divalent linking group in which one or more ring members constituting the ring W1 are heteroatoms, carbonyl carbon atoms, or a combination thereof.

[0132] R 1A and R 1B each independently represents a hydrogen atom, an organic group, a halogen atom, or a cyano group. However, at least one of R 1A and R 1B represents an organic group, a halogen atom, or a cyano group.

[0133] R 2A and R 2B each independently represents a hydrogen atom, an organic group, a halogen atom, or a cyano group. However, at least one of R 2A and R 2B represents an organic group, a halogen atom, or a cyano group.

[0134] p represents 0 or 1, and q represents 0 or 1.

[0135] However, p + q represents 1 or 2.

[0136] R1 and R2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. However, at least one of R1 and R2 represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0137] n represents 0 or 1.

[0138] R3 and R4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0139] m represents an integer of 0 or 1 or more.

[0140] When m represents an integer of 1 or more, n represents 1.

[0141] L represents a carbonyl bond or an ester bond.

[0142] l represents 0 or 1.

[0143] When l represents 1, n represents 1.

[0144] When l represents 1, at least two of R5 to R9 may be connected to each other to form a ring.

[0145] When l represents 0, m represents 0 and n represents 0.

[0146] R5, R6, R7, R8 and R9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or a cycloalkylthio group.

[0147] Z represents an anion.

[0148] By adopting the above constitution, the present invention can achieve extremely excellent storage stability.

[0149] Although the reason is not clear, it can be speculated as follows.

[0150] First, the compound (photoacid generator) represented by the general formula (1) satisfies "However, at least one of R 1A and R 1B represents an organic group, a halogen atom or a cyano group.", "However, at least one of R 2A and R 2B represents an organic group, a halogen atom or a cyano group." and "p represents 0 or 1, and q represents 0 or 1. However, p + q represents 1 or 2.", and there is at least one of R 1A 、R 1B 、R 2A and R 2B on the sulfonium ring that can function as a steric hindrance.

[0151] In addition, regarding the bond between the benzene ring and the sulfonium ring, when l = m = n = 0 is represented, the benzene ring and the sulfonium ring are bonded by a single bond, and the benzene ring can function as a steric hindrance especially from the sulfonium cation side of the sulfonium ring. And when the relationship of l, m and n is other than the above, n = 1, and the alkyl group, cycloalkyl group, halogen atom, cyano group or aryl group that is at least one of R1 and R2 is the same, and can function as a steric hindrance especially from the sulfonium cation side of the sulfonium ring.

[0152] Thus, in the photoacid generator represented by the general formula (1), a group that can function as a steric hindrance exists on and near the sulfonium ring. Therefore, compared with a photoacid generator that does not satisfy the general formula (1), when the resist composition is stored over time, the sulfonium ring (especially the ring members of the sulfonium ring) is less likely to be attacked by other components (e.g., nucleophilic attack, etc.).

[0153] As a result, first, it is considered that the structure of the photoacid generator represented by the general formula (1) is easily maintained without change in the resist composition.

[0154] In addition, by configuring at least one of R 1A , R 1B , R 2A and R 2B that can function as a steric hindrance on the sulfonium ring to be the above general formula (1), and an unsubstituted carbon atom is adjacent to the sulfonium cation in the sulfonium ring. Although the detailed reasons and the like are not clear, the inventors have surprisingly found that the stability of the photoacid generator in the resist composition is greatly improved.

[0155] Therefore, it is speculated that the stability over time of the radiation-sensitive or radiation-sensitive resin composition of the present invention is very excellent.

[0156] The radiation-sensitive or radiation-sensitive resin composition according to the present invention is preferably a so-called resist composition, and can also be a positive resist composition or a negative resist composition. And it can be a resist composition for alkaline development or a resist composition for organic solvent development.

[0157] The composition of the present invention is typically preferably a chemically amplified resist composition.

[0158] Hereinafter, the details of each component contained in the radiation-sensitive or radiation-sensitive resin composition (also simply referred to as "composition") according to the present invention will be described.

[0159] <(B) A compound represented by the general formula (1) that generates an acid upon irradiation with actinic rays or radiation>

[0160] The composition of the present invention contains (B) a compound represented by the general formula (1) that generates an acid upon irradiation with actinic rays or radiation (hereinafter, also referred to as "photoacid generator (B)", "compound (B)").

[0161] In the above general formula (1), Q represents a divalent linking group in which one or more ring members constituting the ring W1 are heteroatoms, carbonyl carbon atoms, or a combination thereof. Among the divalent linking groups as Q, one or more ring members constituting the ring W1 become heteroatoms, carbonyl carbon atoms, or a combination thereof.

[0162] Heteroatoms represent atoms other than carbon atoms, and there is no particular limitation. For example, nitrogen atoms, oxygen atoms, and sulfur atoms can be cited.

[0163] The carbonyl carbon atom represents the carbon atom in the carbonyl bond.

[0164] Q is not particularly limited and is preferably any linking group selected from the following groups.

[0165] [Chemical formula 8]

[0166]

[0167] In the above groups,

[0168] R 11 represents a hydrogen atom or a substituent.

[0169] * represents the bonding bond with the group adjacent to Q that forms ring W1 in the general formula (1).

[0170] As the substituent of R 11 , there is no particular limitation. For example, alkylsulfonyl groups, alkylcarbonyl groups, and alkyl groups can be cited.

[0171] The alkyl group in the alkylsulfonyl group can be linear or branched. For example, alkyl groups having 1 to 6 carbon atoms can be cited, and preferably alkyl groups having 1 to 4 carbon atoms.

[0172] The alkyl group in the alkylcarbonyl group can be linear or branched. For example, alkyl groups having 1 to 6 carbon atoms can be cited, and preferably alkyl groups having 1 to 4 carbon atoms.

[0173] The alkyl group can be linear or branched. For example, alkyl groups having 1 to 6 carbon atoms can be cited, and preferably alkyl groups having 1 to 4 carbon atoms.

[0174] The alkylsulfonyl group, alkylcarbonyl group, and alkyl group can further have substituents.

[0175] * represents the bonding bond with the group adjacent to Q that forms ring W1 in the general formula (1).

[0176] In addition, * only needs to be bonded to any one of the two groups adjacent to Q that forms ring W1 in the general formula (1).

[0177] Q is preferably any linking group selected from the following groups.

[0178] [Chemical formula 9]

[0179]

[0180] In the above formula,

[0181] R11 represents a hydrogen atom or a substituent.

[0182] * represents a bonding site of a group adjacent to Q that forms ring W1 in the general formula (1).

[0183] R 11 and * are as described above, respectively.

[0184] R 1A and R 1B each independently represents a hydrogen atom, an organic group, a halogen atom, or a cyano group.

[0185] R 2A and R 2B each independently represents a hydrogen atom, an organic group, a halogen atom, or a cyano group.

[0186] As R 1A , R 2A , R 1B and R 2B the organic groups are not particularly limited. For example, they represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkylcarbonyl group.

[0187] As the alkyl group, it is not particularly limited and can be linear or branched. Preferably, an alkyl group having 1 to 20 carbon atoms can be cited.

[0188] As the alkyl group, it is more preferably an alkyl group having 1 to 15 carbon atoms, and further preferably an alkyl group having 1 to 10 carbon atoms.

[0189] The alkyl group may have a substituent. The substituent is not particularly limited. For example, the above-mentioned substituent T can be cited.

[0190] As the cycloalkyl group, it can be monocyclic or polycyclic and is not particularly limited. Preferably, a cycloalkyl group having 3 to 20 carbon atoms is used. Specifically, as the cycloalkyl group, cyclopentyl, cyclohexyl, and decahydronaphthyl can be cited.

[0191] As the cycloalkyl group, it is more preferably a cycloalkyl group having 3 to 15 carbon atoms, and further preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0192] The cycloalkyl group may have a substituent. The substituent is not particularly limited. For example, the above-mentioned substituent T can be cited.

[0193] As the alkoxy group, it is not particularly limited. Preferably, an alkoxy group having 1 to 20 carbon atoms is used, more preferably an alkoxy group having 1 to 15 carbon atoms, and further preferably an alkoxy group having 1 to 10 carbon atoms.

[0194] The alkoxy group may have a substituent. The substituent is not particularly limited. For example, the above-mentioned substituent T can be cited.

[0195] The cycloalkyl group in the cycloalkyloxy group can be monocyclic or polycyclic, and there is no particular limitation. It is preferably a cycloalkyl group having 3 to 20 carbon atoms. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0196] The cycloalkyl group in the cycloalkyloxy group is more preferably a cycloalkyl group having 3 to 15 carbon atoms, and still more preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0197] The cycloalkyloxy group may have a substituent. There is no particular limitation on the substituent, and for example, the above-mentioned substituent T can be cited.

[0198] The aryl group is not particularly limited, and is preferably an aryl group having 6 to 20 carbon atoms. Specific examples thereof include phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, condensed tetraphenyl, and fluorenyl.

[0199] The aryl group is more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.

[0200] The aryl group may have a substituent. There is no particular limitation on the substituent, and for example, the above-mentioned substituent T can be cited.

[0201] The alkyl group in the alkylcarbonyl group is not particularly limited, and may be linear or branched. Preferably, an alkyl group having 1 to 20 carbon atoms can be cited.

[0202] The alkyl group in the alkylcarbonyl group is more preferably an alkyl group having 1 to 15 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms.

[0203] The alkylcarbonyl group may have a substituent. There is no particular limitation on the substituent, and for example, the above-mentioned substituent T can be cited.

[0204] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0205] R 1A and R 1B preferably represent a hydrogen atom, an organic group, or a halogen atom, and more preferably represent a hydrogen atom or an organic group.

[0206] R 2A and R 2B preferably represent a hydrogen atom, an organic group, or a halogen atom, and more preferably represent a hydrogen atom or an organic group.

[0207] Among them, at least one of R 1A and R 1B represents an organic group, a halogen atom, or a cyano group, and at least one of R 2A and R 28 represents an organic group, a halogen atom, or a cyano group.

[0208] p represents 0 or 1, and q represents 0 or 1.

[0209] However, p + q represents 1 or 2.

[0210] At least one carbon atom adjacent to Q in the ring W1 has an organic group, a halogen atom, or a cyano group as a substituent.

[0211] R 1A 、R 2A 、R 1B and R 2B do not all represent hydrogen atoms.

[0212] W1 represents a ring.

[0213] In the above general formula (1), W1 represents a ring. W1 is a ring with 5 or more members.

[0214] The upper limit value of the ring members of the ring represented by W1 is not particularly limited, and W1 is preferably a ring with 10 or fewer members.

[0215] W1 is preferably a 6- to 8-membered ring, preferably represents a 6- or 7-membered ring, and more preferably represents a 6-membered ring.

[0216] R1 and R2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. However, at least one of R1 and R2 represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0217] The alkyl group as R1 and R2 is not particularly limited, and may be linear or branched, and preferably, an alkyl group having 1 to 20 carbon atoms can be cited.

[0218] As the alkyl group, it is more preferably an alkyl group having 1 to 15 carbon atoms, and further preferably an alkyl group having 1 to 10 carbon atoms.

[0219] The alkyl group may have a substituent. The substituent is not particularly limited, and for example, the above-mentioned substituent T can be cited.

[0220] The cycloalkyl group as R1 and R2 may be monocyclic or polycyclic, and is not particularly limited, and is preferably a cycloalkyl group having 3 to 20 carbon atoms. Specifically, as the cycloalkyl group, cyclopentyl, cyclohexyl, and decahydronaphthyl can be cited.

[0221] As the cycloalkyl group, it is more preferably a cycloalkyl group having 3 to 15 carbon atoms, and further preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0222] The cycloalkyl group may have a substituent. The substituent is not particularly limited, and for example, the above-mentioned substituent T can be cited.

[0223] The aryl group for R1 and R2 is not particularly limited, and is preferably an aryl group having 6 to 20 carbon atoms. Specifically, phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, condensed tetraphenyl, and fluorenyl can be mentioned.

[0224] As the aryl group, it is more preferably an aryl group having 6 to 15 carbon atoms, and further preferably an aryl group having 6 to 10 carbon atoms.

[0225] The aryl group may have a substituent. The substituent is not particularly limited, and for example, the above-mentioned substituent T can be mentioned.

[0226] As the halogen atom for R1 and R2, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be mentioned.

[0227] R1 and R2 are preferably a hydrogen atom, an alkyl group, or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group. R1 represents a hydrogen atom, and R2 is further preferably an alkyl group.

[0228] R3 and R4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0229] The alkyl group for R3 and R4 is the same as the alkyl group described above for R1 and R2.

[0230] The cycloalkyl group for R3 and R4 is the same as the cycloalkyl group described above for R1 and R2.

[0231] The aryl group for R3 and R4 is the same as the aryl group described above for R1 and R2.

[0232] As the halogen atom for R3 and R4, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be mentioned.

[0233] R3 and R4 are preferably a hydrogen atom, an alkyl group, or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group. R3 and R4 are further preferably a hydrogen atom.

[0234] m represents 0 or an integer of 1 or more.

[0235] The upper limit value of m is not particularly limited, and m is preferably an integer of 5 or less. m is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0236] When m represents an integer of 1 or more, n represents 1.

[0237] L represents a carbonyl bond or an ester bond. As L, a carbonyl bond is preferred.

[0238] When l represents 1, n represents 1.

[0239] When l represents 0, m represents 0 and n represents 0.

[0240] R5, R6, R7, R8 and R9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or a cycloalkylthio group.

[0241] The alkyl group for R5, R6, R7, R8 and R9 is the same as the alkyl group described above for R 1A , R 2A , R 1B and R 2B as described.

[0242] The cycloalkyl group for R5, R6, R7, R8 and R9 is the same as the cycloalkyl group described above for R 1A , R 2A , R 1B and R 2B as described.

[0243] The aryl group for R5, R6, R7, R8 and R9 is the same as the aryl group described above for R 1A , R 2A , R 1B and R 2B as described.

[0244] The alkoxy group for R5, R6, R7, R8 and R9 is the same as the alkoxy group described above for R 1A , R 2A , R 1B and R 2B as described.

[0245] The cycloalkoxy group for R5, R6, R7, R8 and R9 is the same as the cycloalkoxy group described above for R 1A , R 2A , R 1B and R 2B as described.

[0246] The alkoxy group in the alkoxycarbonyl group for R5, R6, R7, R8 and R9 is the same as the alkoxy group described above for R 1A , R 2A , R 1B and R 2B as described.

[0247] The cycloalkyl group in the cycloalkoxycarbonyl group for R5, R6, R7, R8 and R9 is the same as the cycloalkyl group described above for R 1A , R 2A , R 1B and R 2B as described.

[0248] The alkyl group in the alkylcarbonyloxy group of R5, R6, R7, R8 and R9 is the same as the alkyl group described above as R 1A , R 2A , R 1B and R 2B .

[0249] The cycloalkyl group in the cycloalkylcarbonyloxy group of R5, R., R7, R8 and R9 is the same as the cycloalkyl group described above as R 1A , R 2A , R 1B and R 2B .

[0250] The alkyl group in the alkylthio group of R5, R6, R7, R8 and R9 is the same as the alkyl group described above as R 1A , R 2A , R 1B and R 2B .

[0251] The cycloalkyl group in the cycloalkylthio group of R5, R6, R7, R8 and R9 is the same as the cycloalkyl group described above as R 1A , R 2A , R 1B and R 2B .

[0252] The alkenyl group of R5, R6, R7, R8 and R9 is not particularly limited and may be linear or branched, and an alkenyl group having 2 to 20 carbon atoms is preferably cited.

[0253] As the alkenyl group, an alkenyl group having 2 to 15 carbon atoms is more preferably, and an alkenyl group having 2 to 10 carbon atoms is further preferably.

[0254] The alkenyl group may have a substituent. The substituent is not particularly limited, and for example, the above-mentioned substituent T may be cited.

[0255] Examples of the halogen atom of R5, R6, R7, R8 and R9 include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0256] R5, R6, R7, R8 and R9 preferably represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably represent a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and further preferably represent an alkoxy group, a cycloalkoxy group.

[0257] When l represents 1, at least two of R5 to R9 may be connected to each other to form a ring.

[0258] The ring formed by connecting at least two of R5 to R9 to each other is not particularly limited, and examples thereof include aromatic or non-aromatic (e.g., aliphatic) hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensed rings formed by combining two or more of these rings. As the ring structure (in the case of a polycyclic condensed ring, the ring structure of the monocyclic rings constituting it), 3- to 10-membered rings can be mentioned, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0259] Z - represents an anion.

[0260] The anion as Z is not particularly limited, and a non-nucleophilic anion is preferred. For example, sulfonate anions, carboxylate anions, sulfonylimide anions, bis(alkylsulfonyl)imide anions, tris(alkylsulfonyl)methyl anions, etc. can be mentioned.

[0261] A non-nucleophilic anion is an anion with a significantly low ability to cause a nucleophilic reaction and is an anion that can inhibit the decomposition over time caused by an intramolecular nucleophilic reaction. Thereby, the stability of the composition over time is improved.

[0262] As the sulfonate anion, for example, aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc. can be mentioned.

[0263] As the carboxylate anion, for example, aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc. can be mentioned.

[0264] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion can be an alkyl group or a cycloalkyl group. Preferably, an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms can be mentioned. As the aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion, an aryl group having 6 to 14 carbon atoms is preferred, and examples thereof include a phenyl group, a tolyl group, a naphthyl group, etc.

[0265] The alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and the aromatic sulfonate anion can have substituents.

[0266] As other non-nucleophilic anions, for example, phosphonium fluoride (e.g., PF6 - ), boron fluoride (e.g., BF4 - ), antimony fluoride, etc. (e.g., SbF6 - ) can be mentioned.

[0267] As the anion of Z, an aliphatic sulfonate anion in which at least the α-position of a sulfonic acid is substituted with a fluorine atom, a fluorine atom, an aromatic sulfonate anion substituted with a group having a fluorine atom, a bis(alkylsulfonyl)imide anion in which an alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methylide anion in which an alkyl group is substituted with a fluorine atom is preferred. As the non-nucleophilic anion, a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms or a benzenesulfonate anion having a fluorine atom is more preferred, and a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is even more preferred.

[0268] In general formula (1), Z is preferably an anion represented by any one of the following general formulas (3) to (5).

[0269] [Chemical formula 10]

[0270]

[0271] In general formula (3),

[0272] Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

[0273] L1 represents a single bond or a divalent linking group.

[0274] A represents a monovalent organic group.

[0275] x represents an integer of 1 to 20.

[0276] [Chemical formula 11]

[0277]

[0278] In general formula (4),

[0279] Xf1 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Two Xf1s may be connected to each other to form a ring structure.

[0280] [Chemical formula 12]

[0281]

[0282] In general formula (5),

[0283] Xf2 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Two Xf2s may be connected to each other to form a ring structure.

[0284] The number of carbon atoms of the alkyl group in the alkyl group substituted with at least one fluorine atom as Xf is preferably 1 to 10, more preferably 1 to 4. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0285] The alkyl group substituted with at least one fluorine atom may have substituents. There is no particular limitation on the substituents, and for example, the above-mentioned substituent T can be cited.

[0286] As the divalent linking group for L1, for example, -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 formed by combining multiple of them can be cited.

[0287] Among them, alkylene, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -SO2-alkylene-, -COO-alkylene-, -alkylene-COO-, -OCO-alkylene-, -alkylene-OCO-, -CONH-alkylene- or -NHCO-alkylene- are preferred, and alkylene, -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene-, -alkylene-COO-, -OCO-alkylene- or -alkylene-OCO- are more preferred.

[0288] Alkylene, cycloalkylene, and alkenylene may have substituents. There is no particular limitation on the substituents, and for example, the above-mentioned substituent T can be cited, and a fluorine atom is preferred.

[0289] A represents an organic group.

[0290] There is no particular limitation on the number of carbon atoms of the organic group, generally 1 to 30, and preferably 1 to 20.

[0291] There is no particular limitation on the organic group, and for example, alkyl, alkoxy, etc. can be cited.

[0292] There is no particular limitation on the alkyl group, which can be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.

[0293] There is no particular limitation on the alkoxy group, preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and further preferably an alkoxy group having 1 to 4 carbon atoms.

[0294] The alkyl group and the alkoxy group may have substituents. As the substituents, there is no particular limitation, and for example, the above-mentioned substituent T can be cited, and a fluorine atom is preferred.

[0295] Moreover, A may represent an organic group containing a cyclic structure. Among them, a cyclic organic group is preferred.

[0296] As the cyclic organic group, for example, an alicyclic group, an aryl group, and a heterocyclic group can be mentioned.

[0297] The alicyclic group can be monocyclic or polycyclic. As the monocyclic alicyclic group, for example, monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl can be mentioned. As the polycyclic alicyclic group, for example, polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl can be mentioned. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl are preferred.

[0298] The aryl group can be monocyclic or polycyclic. As the aryl group, for example, phenyl, naphthyl, phenanthryl, and anthryl can be mentioned.

[0299] The heterocyclic group can be monocyclic or polycyclic. The polycyclic heterocyclic group can more effectively inhibit the diffusion of acid. Also, the heterocyclic group can have aromaticity or non-aromaticity. As the heterocycle having aromaticity, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring can be mentioned. As the heterocycle not having aromaticity, for example, tetrahydropyran ring, lactone ring, sultone ring, and decahydroisoquinoline ring can be mentioned. As an example of the lactone ring and the sultone ring, the lactone structure and the sultone structure exemplified in the aforementioned resin can be mentioned. Among the heterocycles in the heterocyclic group, furan ring, thiophene ring, pyridine ring, or decahydroisoquinoline ring is particularly preferred.

[0300] The above cyclic organic group can have a substituent. As the substituent, for example, an alkyl group (which can be either straight-chain or branched-chain, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which can be either 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 urethane group, a urea group, a thioether group, a sulfonamide group, and a sulfonate group can be mentioned. In addition, the carbon (the carbon contributing to the formation of the ring) constituting the cyclic organic group can be a carbonyl carbon.

[0301] The alkyl group in which at least one fluorine atom substitutes Xf1 is the same as the alkyl group in which at least one fluorine atom substitutes Xf described above.

[0302] The alkyl group in which at least one fluorine atom substitutes Xf2 is the same as the alkyl group in which at least one fluorine atom substitutes Xf described above.

[0303] The compound represented by the above general formula (1) is preferably a compound represented by the following general formula (2).

[0304] [Chemical Formula 13]

[0305]

[0306] In general formula (2),

[0307] Ra to Rd each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0308] However, at least one of Ra to Rd represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0309] Q has the same meaning as Q in the above general formula (1).

[0310] R1 and R2 have the same meanings as R1 and R2 in the above general formula (1).

[0311] R5, R6, R7, R8, and R9 have the same meanings as R5, R6, R7, R8, and R9 in the above general formula (1).

[0312] At least two of R5 to R9 may be connected to each other to form a ring.

[0313] Z has the same meaning as Z- in the above general formula (1).

[0314] The alkyl group as Ra to Rd is the same as the alkyl group described as R 1A , R 2A , R 1B and R 2B above.

[0315] The cycloalkyl group as Ra to Rd is the same as the cycloalkyl group described as R 1A , R 2A , R 1B and R 2B above.

[0316] The aryl group as Ra to Rd is the same as the aryl group described as R 1A , R 2A , R 1B and R 2B above.

[0317] The halogen atom as Ra to Rd is the same as the halogen atom described as R 1A , R 2A , R 1B and R 2B above.

[0318] Ra to Rd preferably represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a halogen atom, more preferably a hydrogen atom, an alkyl group, or a cycloalkyl group.

[0319] At least two of R5 to R9 may be connected to each other to form a ring.

[0320] The ring formed by connecting at least two of R5 to R9 to each other is not particularly limited, and examples thereof include aromatic or non-aromatic (e.g., aliphatic) hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. As the ring structure (in the case of a polycyclic condensed ring, the ring structure of the monocyclic rings constituting it), a 3- to 10-membered ring can be mentioned, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

[0321] As a preferred embodiment, in general formula (1) or general formula (2), at least one of R5 to R9 preferably represents an alkoxy group, a cycloalkoxy group, an alkylthio group, or a cycloalkylthio group, and more preferably represents an alkoxy group or a cycloalkoxy group.

[0322] Specific examples of the compound represented by general formula (1) are shown below, but the present invention is not limited to these specific examples. t Bu represents tert-butyl, and Et represents ethyl. n Bu represents n-butyl.

[0323] [Chemical formula 14]

[0324]

[0325] [Chemical formula 15]

[0326]

[0327] Within the range not impairing the effects of the present invention, other photoacid generators can be used in addition to the compound represented by general formula (1).

[0328] The photoacid generator can be in the form of a low-molecular compound or in the form of being incorporated into a part of a polymer. Further, the form of a low-molecular compound and the form of being incorporated into a part of a polymer can be used in combination.

[0329] The photoacid generator is preferably in the form of a low-molecular compound.

[0330] When the photoacid generator is in the form of a low-molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

[0331] When the photoacid generator is in the form of being incorporated into a part of a polymer, it can be incorporated into a part of the resin (A) described below or into a resin different from the resin (A).

[0332] The photoacid generator can be used alone as one kind or two or more kinds can be used in combination.

[0333] The content of the photoacid generator in the composition (the total when there are multiple kinds) is preferably 0.1% by mass to 35% by mass, more preferably 0.5% by mass to 25% by mass, still more preferably 1.0% by mass to 20% by mass, and particularly preferably 1.0% by mass to 20% by mass, based on the total solid content of the composition.

[0334] <(A) resin>

[0335] The radiation-sensitive or radiation-sensitive resin composition according to the present invention contains a resin (A).

[0336] The above resin (A) is typically a resin whose polarity increases by the action of an acid, and preferably a resin whose polarity increases by the action of an acid and whose solubility in a developer changes.

[0337] The above resin (resin (A)) whose polarity increases by the action of an acid is preferably a resin obtained by polymerizing at least an ethylenically unsaturated compound.

[0338] The above ethylenically unsaturated compound preferably has 1 to 4 ethylenically unsaturated bonds, and more preferably 1. In addition, the above ethylenically unsaturated compound is preferably a monomer as a monomer.

[0339] Moreover, the molecular weight of the above ethylenically unsaturated compound is preferably 28 to 1,000, more preferably 50 to 800, and still more preferably 100 to 600.

[0340] Moreover, the resin whose polarity increases by the action of an acid preferably has an acid-decomposable group, and more preferably a resin containing a structural unit having an acid-decomposable group.

[0341] In this case, in the pattern forming method according to the present invention described later, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0342] 〔Structural unit having an acid-decomposable group〕

[0343] Resin (A) preferably contains a structural unit having an acid-decomposable group (also referred to as a "repeating unit").

[0344] As resin (A), known resins can be appropriately used. For example, known resins disclosed in paragraphs 0055 to 0191 of the specification of US Patent Application Publication No. 2016 / 0274458, paragraphs 0035 to 0085 of the specification of US Patent Application Publication No. 2015 / 0004544, and paragraphs 0045 to 0090 of the specification of US Patent Application Publication No. 2016 / 0147150 can be preferably used as resin (A).

[0345] The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that is decomposed and detached by the action of an acid.

[0346] Examples of the polar group include acidic groups (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, a sulfimide group, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tris(alkylcarbonyl)methylene, and tris(alkylsulfonyl)methylene, and an alcohol hydroxyl group.

[0347] In addition, the alcohol hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group), excluding an aliphatic alcohol group in which the α-position of the hydroxyl group is substituted with an electron-withdrawing group such as a fluorine atom (e.g., hexafluoroisopropanol group). As the alcohol hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less is preferred.

[0348] Preferred polar groups include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group.

[0349] Preferred groups as the acid-decomposable group are groups in which a hydrogen atom of these groups is substituted with a group (leaving group) that is detached by the action of an acid.

[0350] Examples of the group (leaving group) that is detached by the action of an acid include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), and -C(R 01 )(R 02 )(OR 39 ), etc.

[0351] In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R 36 and R 37 may bond to each other to form a ring.

[0352] R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0353] R 36 to R 39 , R 01 and R02 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.

[0354] R 36 ~R 39 , R 01 and R 02 The cycloalkyl group may be a monocyclic group or a polycyclic group. As a monocyclic group, a cycloalkyl group having 3 to 8 carbon atoms is preferred, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. As a polycyclic group, a cycloalkyl group having 6 to 20 carbon atoms is preferred, and examples thereof include adamantyl, norbornyl, isobornyl, camphenyl, dicyclopentyl, α-pinenyl, tricyclodecyl, tetracyclododecyl, and androstanyl. In addition, at least one carbon atom in the cycloalkyl group may be substituted by a heteroatom such as an oxygen atom.

[0355] 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.

[0356] 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.

[0357] R 36 ~R 39 , R 01 and R 02 The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl group, allyl group, butenyl group, and cyclohexenyl group.

[0358] As R 36 With R 37 The ring formed by bonding to each other is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0359] The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, or the like, and more preferably an acetal group or a tertiary alkyl ester group.

[0360] The resin (A) preferably has a structural unit represented by the following formula AI as a structural unit having an acid-decomposable group.

[0361] [Chemical formula 16]

[0362]

[0363] In formula AI, Xa 1 represents a halogen atom other than a hydrogen atom or a fluorine atom, or a monovalent organic group, T represents a single bond or a divalent linking group, Rx 1 to Rx 3 each independently represents an alkyl group or a cycloalkyl group, and any two of Rx 1 to Rx 3 can be bonded to form a ring structure, or may not form a ring structure.

[0364] Examples of the divalent linking group as 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.

[0365] T is preferably a single bond or -COO-Rt-. Rt is preferably a linear alkylene group having 1 to 5 carbon atoms, more preferably -CH2-, -(CH2)2-, or -(CH2)3-. T is more preferably a single bond.

[0366] Xa 1 is preferably a hydrogen atom or an alkyl group.

[0367] Xa 1 The alkyl group of can have substituents, and examples of the substituents include halogen atoms other than a hydroxyl group and a fluorine atom.

[0368] Xa 1 The alkyl group of is preferably an alkyl group having 1 to 4 carbon atoms, and examples include a methyl group, an ethyl group, a propyl group, and a hydroxymethyl group. Xa 1 The alkyl group of is preferably a methyl group.

[0369] As Rx 1 、Rx 3 and Rx 3 The alkyl groups of and can be linear or branched, and preferably include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, etc. As the number of carbon atoms of the alkyl group, it is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. Rx 1 、Rx 2 and Rx 3 In the alkyl groups of, a part of the carbon-carbon bond can be a double bond.

[0370] As Rx 1 、Rx 2 and Rx 3 The cycloalkyl groups of and are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

[0371] As Rx 1 、Rx 2 and Rx 3 A ring structure formed by bonding two of them, preferably a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, or a polycyclic cycloalkyl ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, and an adamantane ring. More preferably, it is a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring. As Rx 1 、Rx 2 and Rx 3 The ring structure formed by bonding two of them is also preferably the structure shown below.

[0372] [Chemical formula 17]

[0373]

[0374] Specific examples of the monomer corresponding to the structural unit represented by formula AI are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to Xa in formula AI 1 In the case of being methyl, Xa 1 Can be arbitrarily substituted with a halogen atom other than a hydrogen atom and a fluorine atom or a monovalent organic group.

[0375] [Chemical formula 18]

[0376]

[0377] As the structural unit having an acid-decomposable group, the resin (A) also preferably has the structural unit described in paragraphs 0336 to 0369 of the specification of US Patent Application Publication No. 2016 / 0070167.

[0378] Furthermore, the resin (A) may have, as the structural unit having an acid-decomposable group, the structural unit containing a group that decomposes by the action of an acid to generate an alcohol hydroxyl group described in paragraphs 0363 to 0364 of the specification of US Patent Application Publication No. 2016 / 0070167.

[0379] Furthermore, the resin (A) preferably contains a repeating unit having a structure (acid-decomposable group) in which a phenolic hydroxyl group is protected by a leaving group that decomposes by the action of an acid as the repeating unit having an acid-decomposable group. In addition, in the present specification, a phenolic hydroxyl group is a group obtained by substituting a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

[0380] As the leaving group that decomposes by the action of an acid, for example, groups represented by formulas (Y1) to (Y4) can be mentioned.

[0381] Formula (Y1): -C(Rx1)(Rx2)(Rx3)

[0382] Formula (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0383] Formula (Y3): -C(R 36 )(R 37 )(OR 38 )

[0384] Formula (Y4): -C(Rn)(H)(Ar)

[0385] In Formula (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Among them, when all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferred that at least 2 of Rx1 to Rx3 are methyl groups.

[0386] Among them, Rx1 to Rx3 are each independently more preferably a repeating unit representing a linear or branched alkyl group, and Rx1 to Rx3 are each independently further preferably a repeating unit representing a linear alkyl group.

[0387] Two of Rx1 to Rx3 may also be bonded to form a monocyclic or polycyclic ring.

[0388] As the alkyl group of Rx1 to Rx3, preferred are alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0389] As the cycloalkyl group of Rx1 to Rx3, preferred are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl.

[0390] As the cycloalkyl group formed by bonding two of Rx1 to Rx3, preferred are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl. Among them, more preferred is a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0391] In 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 group having a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group.

[0392] The groups represented by Formula (Y1) and (Y2) are preferably, for example, in a manner where Rx1 is methyl or ethyl, and Rx2 and Rx3 are bonded to form the above cycloalkyl group.

[0393] In Formula (Y3), R 36 ~R 38Each independently represents a hydrogen atom or a monovalent organic group. R 37 and R 38 may bond to each other to form a ring. As the monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. may be mentioned. R 36 is preferably a hydrogen atom.

[0394] 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 bond to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0395] As a repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and detached by the action of an acid (acid-decomposable group), a repeating unit having a structure in which a hydrogen atom in the phenolic hydroxyl group is protected by a group represented by formula (Y1) to (Y4) is preferred.

[0396] As a repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and detached by the action of an acid (acid-decomposable group), a repeating unit represented by the following general formula (AII) is preferred.

[0397] [Chemical formula 19]

[0398]

[0399] In general formula (AII),

[0400] 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. Among them, R 62 may bond to Ar6 to form a ring, and at this time, R 62 represents a single bond or an alkylene group.

[0401] X6 represents a single bond, -COO- or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group.

[0402] L6 represents a single bond or an alkylene group.

[0403] Ar6 represents an (n + 1)-valent aromatic hydrocarbon group, and when it bonds to R 62 to form a ring, it represents an (n + 2)-valent aromatic hydrocarbon group.

[0404] When n ≥ 2, Y2 each independently represents a hydrogen atom or a group that is detached by the action of an acid. Among them, at least one of Y2 represents a group that is detached by the action of an acid. As the group that is detached by the action of an acid of Y2, formula (Y1) to (Y4) is preferred.

[0405] n represents an integer of 1 to 4.

[0406] 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), etc. Preferably, it is a group having 8 or less carbon atoms.

[0407] [Chemical formula 20]

[0408]

[0409] [Chemical formula 21]

[0410]

[0411] The resin (A) may contain, alone, one kind of structural unit having an acid-decomposable group, or may contain two or more kinds.

[0412] The content of the structural unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of structural units having an acid-decomposable group, it is the total thereof) is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 80 mol%, and still more preferably 15 mol% to 70 mol% with respect to all the structural units of the resin (A).

[0413] In addition, in the present invention, when the content of the "structural unit" is specified in terms of molar ratio, the above "structural unit" has the same meaning as the "monomer unit". And in the present invention, the above "monomer unit" can be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0414] [Structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure]

[0415] The resin (A) preferably contains a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0416] As a lactone structure or a sultone structure, as long as it has a lactone structure or a sultone structure, any one of them can be used. Preferably, it is a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. More preferably, it is a structure formed by fusing a 5- to 7-membered ring lactone structure with another ring structure to form a bicyclic structure or a spiro structure, or a structure formed by fusing a 5- to 7-membered ring sultone structure with another ring structure to form a bicyclic structure or a spiro structure. Further preferably, it contains a structural unit having a lactone structure represented by any one of the following formulas LC1-1 to LC1-21 or a sultone structure represented by any one of the following formulas SL1-1 to SL1-3. And the lactone structure or the sultone structure can be directly bonded to the main chain. Preferred structures are LC1-1, LC1-4, LC1-5, LC1-8, LC1-16, LC1-21, SL1-1.

[0417] [Chemical formula 22]

[0418]

[0419] The lactone structure part or the sultone structure part may have a substituent (Rb 2 ), or may not have a substituent (Rb 2 ). As preferred substituents (Rb 2 ), examples include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom other than a fluorine atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferably, they are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, multiple substituents (Rb 2 ) may be the same or different. And multiple substituents (Rb 2 ) may bond to each other to form a ring.

[0420] The structural unit having a lactone structure or a sultone structure is preferably a structural unit represented by the following formula III.

[0421] And the resin containing a structural unit having an acid-decomposable group preferably contains a structural unit represented by the following formula III.

[0422] [Chemical formula 23]

[0423]

[0424] In the above formula III,

[0425] A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).

[0426] n is the number of repetitions of the structure represented by -R 0 -Z-, and represents an integer from 0 to 5, preferably 0 or 1, more preferably 0. When n is 0, there is no -R 0 -Z-, and A and R 8 are bonded by a single bond.

[0427] R 0 represents an alkylene group, a cycloalkylene group or a combination thereof. R 0 When there are multiple, each independently represents an alkylene group, a cycloalkylene group or a combination thereof.

[0428] Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are multiple Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.

[0429] R 8 represents a monovalent organic group having a lactone structure or a sultone structure.

[0430] R 7 represents a hydrogen atom, a halogen atom other than a fluorine atom or a monovalent organic group (preferably a methyl group).

[0431] R 0 The alkylene group or cycloalkylene group of can have substituents.

[0432] Z is preferably an ether bond or an ester bond, more preferably an ester bond.

[0433] Specific examples of the monomer corresponding to the structural unit represented by Formula III and specific examples of the monomer corresponding to the structural unit represented by Formula A-1 described later are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to R in Formula III 7 and R in Formula A-1 described later A 1 in the case of being a methyl group, but R 7 and R A 1 can be arbitrarily substituted with a hydrogen atom, a halogen atom other than a fluorine atom or a monovalent organic group.

[0434] [Chemical Formula 24]

[0435]

[0436] In addition to the above monomers, the monomers shown below are also preferably used as raw materials for the resin (A).

[0437] [Chemical Formula 25]

[0438]

[0439] The resin (A) may contain a structural unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.

[0440] The structural unit having a cyclic carbonate structure is preferably a structural unit represented by the following formula A-1.

[0441] [Chemical formula 26]

[0442]

[0443] In formula A-1, R A 1 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group), n represents an integer of 0 or more, and R A 2 represents a substituent. When n is 2 or more, R A 2 each independently represents a substituent, A represents a single bond or a divalent linking group, and Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with the group represented by -O-C(=O)-O- in the formula.

[0444] The resin (A) also preferably has a structural unit described in paragraphs 0370 to 0414 of the specification of US Patent Application Publication No. 2016 / 0070167 as a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0445] The resin (A) preferably has a structural unit (a) containing at least two lactone structures (hereinafter, also referred to as "structural unit (a)").

[0446] The at least two lactone structures may be, for example, a structure in which at least two lactone structures are condensed, and may also be a structure in which at least two lactone structures are connected by a single bond or a linking group.

[0447] The lactone structure of the structural unit (a) is not particularly limited, and a 5- to 7-membered ring lactone structure is preferred, and a structure in which another ring structure is condensed in the form of forming a bicyclic structure or a spiro structure in the 5- to 7-membered ring lactone structure is preferred.

[0448] The above lactone structure may be preferably selected, for example, from the lactone structures represented by any one of LC1-1 to LC1-21 above.

[0449] The structural unit having at least two lactone structures (hereinafter, also referred to as "structural unit (a)") is preferably a structural unit represented by the following formula L-1.

[0450] [Chemical formula 27]

[0451]

[0452] In formula L-1, Ra represents a hydrogen atom or an alkyl group, and Rb represents a partial structure having two or more lactone structures.

[0453] The alkyl group of Ra is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group of Ra may be substituted. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom, or alkoxy groups such as a mercapto group, a hydroxyl group, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, and a benzyloxy group, and acetoxy groups such as an acetyl group and a propionyl group. Ra is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0454] Examples of the lactone structure possessed by the Rb partial structure include the above-mentioned lactone structures.

[0455] The partial structure of Rb having two or more lactone structures is preferably a structure in which at least two lactone structures are connected by a single bond or a linking group and a structure in which at least two lactone structures are condensed.

[0456] Hereinafter, the structural unit (a1) of the structure having at least two lactone structures condensed and the structural unit (a2) of the structure having at least two lactone structures connected by a single bond or a linking group will be described separately.

[0457] - Structural unit (a1) of the structure having at least two lactone structures condensed -

[0458] The structure having at least two lactone structures condensed is preferably a structure having two or three lactone structures condensed, and more preferably a structure having two lactone structures condensed.

[0459] The structural unit of the structure having at least two lactone structures condensed (hereinafter, also referred to as "structural unit (a1)") includes, for example, a structural unit represented by the following formula L-2.

[0460] [Chemical formula 28]

[0461]

[0462] In formula L-2, the meaning of Ra is the same as the meaning of Ra in formula L-1, Re1 to Re8 each independently represent a hydrogen atom or an alkyl group, Me1 represents a single bond or a divalent linking group, and Me2 and Me3 each independently represent a divalent linking group.

[0463] The alkyl groups of Re1 to Re8 are preferably 5 or less carbon atoms, and more preferably 1 carbon atom.

[0464] Examples of the alkyl group having 5 or less carbon atoms for Re1 to Re8 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl and the like.

[0465] Among them, Re1 to Re8 are preferably hydrogen atoms.

[0466] Examples of the divalent linking group for Me1 include alkylene, cycloalkylene, -O-, -CO-, -COO-, -OCO- and a group formed by combining two or more of these groups.

[0467] The alkylene of Me1 preferably has 1 to 10 carbon atoms. More preferably, it has 1 or 2 carbon atoms. As the alkylene having 1 or 2 carbon atoms, methylene or vinyl is preferred.

[0468] The alkylene of Me1 may be linear or branched. Examples thereof include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl and the like.

[0469] The cycloalkylene of Me1 preferably has 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms.

[0470] Examples of the cycloalkylene of Me1 include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclodecylene and the like.

[0471] As the divalent linking group of Me1, a group formed by combining two or more of the above groups is preferably a group formed by combining alkylene and -COO-, and a group formed by combining -OCO- and alkylene. Further, a group formed by combining two or more of the above groups is more preferably a group formed by combining methylene and -COO- group, and a group formed by combining -COO- group and methylene.

[0472] Examples of the divalent linking group for Me2 and Me3 include alkylene, -O- and the like. The divalent linking group for Me2 and Me3 is preferably methylene, vinyl, -O-, and more preferably -O-.

[0473] The monomer corresponding to the structural unit (a1) can be synthesized, for example, by the method described in JP-A-2015-160836.

[0474] Hereinafter, specific examples of the structural unit (a1) are shown, but the present invention is not limited thereto. In the following formulas, R9 represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and * represents the bonding position to other structural units.

[0475] [Chemical formula 29]

[0476]

[0477] [Chemical Formula 31]

[0478]

[0479] - The structural unit (a2) in which at least two lactone structures have a structure connected by a single bond or a linking group

[0480] The structure in which at least two lactone structures are connected by a single bond or a linking group is preferably a structure in which 2 to 4 lactone structures are connected by a single bond or a linking group, and more preferably a structure in which 2 lactone structures are connected by a single bond or a linking group.

[0481] Examples of the linking group may include the same groups as those exemplified as the linking group for M2 in the following formula L-3.

[0482] The structural unit (hereinafter, also referred to as "structural unit (a2)") in which two or more lactone structures have a structure connected by a single bond or a linking group may include, for example, the structural unit represented by the following formula L-3.

[0483] [Chemical Formula 32]

[0484]

[0485] In formula L-3, the meaning of Ra is the same as the meaning of Ra in the above formula L-1, M1 and M2 each independently represent a single bond or a linking group, and Lc1 and Lc2 each independently represent a group having a lactone structure.

[0486] Examples of the linking group for M1 may include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of these groups.

[0487] The alkylene group for M1 is preferably, for example, 1 to 10 carbon atoms.

[0488] The alkylene group for M1 may be linear or branched, and examples may include a methylene group, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc.

[0489] The cycloalkylene group for M1 is preferably, for example, 5 to 10 carbon atoms.

[0490] Examples of the cycloalkylene group for M1 may include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclodecylene group, etc.

[0491] As a linking group for M1, a group formed by combining two or more of the above groups is preferably, for example, a group formed by combining an alkylene group and -COO-, and a group formed by combining -OCO- and an alkylene group. Further preferably, a group formed by combining two or more of the above groups is a group formed by combining a methylene group and a -COO- group, and a group formed by combining a -COO- group and a methylene group.

[0492] Examples of the linking group for M2 include the same groups as those exemplified for the linking group for M1.

[0493] The lactone structure of Lc1 is preferably, for example, a 5- to 7-membered ring lactone structure, and in the 5- to 7-membered ring lactone structure, other ring structures are condensed in a form of forming a bicyclic structure or a spiro structure. The above lactone structure is more preferably a lactone structure represented by any one of LC1-1 to LC1-21. As a further preferred lactone structure, LC1-1, LC1-4, LC1-5, LC1-6, LC1-13, LC1-14, and LC1-17 can be mentioned.

[0494] The lactone structure of Lc1 may contain a substituent. Examples of the substituent that the lactone structure of Lc1 may contain include the same substituents as the substituent (Rb2) of the above lactone structure.

[0495] Examples of the lactone structure of Lc2 include the same structures as those exemplified for the lactone structure of Lc1.

[0496] As the structural unit (a2), the structural unit represented by the following formula L-4 is preferably the structural unit represented by the above formula L-3.

[0497] [Chemical formula 33]

[0498]

[0499] In formula L-4, the meaning of Ra is the same as the meaning of Ra in formula L-1 above, Mf1 and Mf2 each independently represent a single bond or a linking group, Rf1, Rf2, and Rf3 each independently represent a hydrogen atom or an alkyl group, Mf1 and Rf1 may bond to each other to form a ring, and Mf2 and Rf2 or Rf3 may bond to each other to form a ring.

[0500] The meaning of the linking group of Mf1 is the same as the meaning of the linking group of M1 in formula L-3 above.

[0501] The meaning of the linking group of Mf2 is the same as the meaning of the linking group of M2 in formula L-3 above.

[0502] The alkyl group of Rf1 may be, for example, an alkyl group having 1 to 4 carbon atoms. The alkyl group of Rf1 having 1 to 4 carbon atoms is preferably methyl or ethyl, more preferably methyl. The alkyl group of Rf1 may have a substituent. Examples of the substituent that the alkyl group of Rf1 may have include alkoxy groups such as hydroxy, methoxy and ethoxy, cyano group, and halogen atoms such as fluorine atom.

[0503] The meanings of the alkyl groups of Rf2 and Rf3 are the same as those of the alkyl group of Rf1.

[0504] Mf1 and Rf1 may bond to each other to form a ring. Examples of the structure in which Mf1 and Rf1 bond to each other to form a ring include the lactone structures represented by LC1-13, LC1-14 or LC1-17 in the above lactone structure.

[0505] Mf2 and Rf2 or Rf3 may bond to each other respectively to form a ring.

[0506] Examples of the structure in which Mf2 and Rf2 bond to each other to form a ring include the lactone structures represented by LC1-7, LC1-8 or LC1-15 in the above lactone structure.

[0507] Examples of the structure in which Mf2 and Rf3 bond to each other to form a ring include the lactone structures represented by any one of LC1-3 to LC1-6 in the above lactone structure.

[0508] Hereinafter, specific examples of the structural unit (a2) are shown, but the present invention is not limited thereto. * indicates the bonding position to other structural units.

[0509] [Chemical formula 34]

[0510]

[0511] The structural unit having at least two lactone structures usually has optical isomers, but any optical isomer can be used. Also, one kind of optical isomer can be used alone, or a plurality of optical isomers can be used in combination. In the case of mainly using one kind of optical isomer, its optical purity (ee) is preferably 90% or more, more preferably 95% or more.

[0512] The content ratio of the structural unit having at least two lactone structures is preferably 10 mol% to 60 mol%, more preferably 20 mol% to 50 mol%, further preferably 30 mol% to 50 mol% based on the total structural units in the resin (A).

[0513] In order to improve the effects in the present invention, it is also possible to use in combination two or more structural units each having at least two lactone structures. When two or more repeating units each having at least two lactone structures are contained, the total content ratio of the structural units each having at least two lactone structures is preferably within the above range.

[0514] The resin (A) may contain a single structural unit having at least one selected from a lactone structure, a sultone structure, and a carbonate structure, or may contain two or more in combination.

[0515] The content of the structural unit having at least one selected from the lactone structure, the sultone structure, and the carbonate structure contained in the resin (A) (the total in the case where there are a plurality of structural units having at least one selected from the lactone structure, the sultone structure, and the carbonate structure) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 65 mol%, and still more preferably 20 mol% to 60 mol% with respect to the total structural units of the resin (A).

[0516] [Structural unit having a polar group]

[0517] The resin (A) preferably contains a structural unit having a polar group.

[0518] Examples of the polar group include a hydroxyl group, a cyano group, and a carboxyl group.

[0519] The structural unit having a polar group is preferably a structural unit having an alicyclic hydrocarbon structure substituted with a polar group. Further, the structural unit having a polar group preferably does not have an acid-decomposable group. As the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group or a norbornyl group is preferable.

[0520] The resin (A) preferably has a carboxyl group.

[0521] Hereinafter, specific examples of the monomer corresponding to the structural unit having a polar group are shown, but the present invention is not limited to these specific examples. Further, the following specific examples are described as methacrylate compounds, but may be acrylate compounds.

[0522] [Chemical formula 35]

[0523]

[0524] In addition, as specific examples of the structural unit having a polar group, the structural units disclosed in paragraphs 0415 to 0433 of the specification of US Patent Application Publication No. 2016 / 0070167 can be cited.

[0525] The resin (A) may contain a single structural unit having a polar group, or may contain two or more in combination.

[0526] The content of the structural unit having a polar group is preferably 5 mol% to 40 mol%, more preferably 5 to 30 mol%, and still more preferably 10 mol% to 25 mol% relative to the structural units in the resin (A).

[0527] [Structural units having neither an acid-decomposable group nor a polar group]

[0528] The resin (A) can further have a structural unit having neither an acid-decomposable group nor a polar group. The structural unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure. As the structural unit having neither an acid-decomposable group nor a polar group, for example, the structural units described in paragraphs 0236 to 0237 of US Patent Application Publication No. 2016 / 0026083 can be cited. The following shows preferred examples of monomers corresponding to the structural unit having neither an acid-decomposable group nor a polar group.

[0529] [Chemical formula 36]

[0530]

[0531] In addition, as a specific example of the structural unit having neither an acid-decomposable group nor a polar group, the structural units disclosed in paragraph 0433 of US Patent Application Publication No. 2016 / 0070167 can be cited.

[0532] The resin (A) may contain a single structural unit having neither an acid-decomposable group nor a polar group, or may contain two or more kinds in combination.

[0533] The content of the structural unit having neither an acid-decomposable group nor a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, and still more preferably 5 to 25 mol% relative to the total structural units in the resin (A).

[0534] (Repeat unit (a1))

[0535] The resin (A) can further have the following repeat unit (a1).

[0536] The repeat unit (a1) is a repeat unit derived from a monomer (also referred to as "monomer a1") having a glass transition temperature of 50°C or lower when made into a homopolymer.

[0537] Moreover, the repeat unit (a1) is a non-acid-decomposable repeat unit. Therefore, the repeat unit (a1) does not have an acid-decomposable group.

[0538] (Method for measuring the glass transition temperature of a homopolymer)

[0539] Regarding the glass transition temperature of the homopolymer, when there are catalog values or literature values, those values are adopted; when there are no catalog values or literature values, differential scanning calorimetry (DSC) is used for measurement. The weight-average molecular weight (Mw) of the homopolymer used for the measurement of Tg is set to 18,000, and the dispersity (Mw / Mn) is set to 1.7. As the DSC apparatus, a Q1000 type heat analysis DSC differential scanning calorimeter manufactured by TA Instruments Japan Inc. is used, and the heating rate is measured at 10 °C / min.

[0540] In addition, the homopolymer used for the measurement of Tg can be synthesized by using the corresponding monomer through a known method, for example, it can be synthesized by a general dropwise polymerization method or the like. An example is shown below.

[0541] 54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was heated to 80 °C under a nitrogen stream. While stirring this liquid, 125 parts by mass of a PGMEA solution containing 21% by mass of the corresponding monomer and 0.35% by mass of dimethyl 2,2'-azobis(isobutyrate) 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 naturally 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: 18,000, Mw / Mn: 1.7). The obtained homopolymer was used for DSC measurement. The DSC apparatus and the heating rate are as described above.

[0542] The monomer a1 is not particularly limited as long as the glass transition temperature (Tg) of the resulting homopolymer is 50 °C or lower. From the viewpoints of improving the resolution of the dot pattern and suppressing the roughness of the sidewalls of the resist pattern that may occur during etching, the Tg of the resulting homopolymer is preferably 30 °C or lower. The lower limit of the Tg of the homopolymer formed from the monomer a1 is not particularly limited, preferably -80 °C or higher, more preferably -70 °C or higher, further preferably -60 °C or higher, and particularly preferably -50 °C or higher. By setting the lower limit of the Tg of the homopolymer formed from the monomer a1 within the above range, the fluidity of the pattern during heating can be suppressed, and the verticality of the dot pattern can be further improved, so it is preferred.

[0543] As the repeating unit (a1), from the viewpoint of being able to more easily volatilize the residual solvent, a repeating unit that can contain a heteroatom in the chain and has a non-acid-decomposable alkyl group with 2 or more carbon atoms is preferred. In this specification, "non-acid-decomposable" means having the property of not undergoing a detachment / decomposition reaction due to the acid generated by the photoacid generator.

[0544] That is, the "non-acid-decomposable alkyl group" more specifically refers to an alkyl group that does not detach from the resin (A) by the action of an acid generated by a photoacid generator or an alkyl group that is not decomposed by the action of an acid generated by a photoacid generator.

[0545] The non-acid-decomposable alkyl group can be either linear or branched.

[0546] Hereinafter, a repeating unit having a non-acid-decomposable alkyl group that may contain a heteroatom in the chain and has 2 or more carbon atoms will be described.

[0547] The non-acid-decomposable alkyl group that may contain a heteroatom in the chain and has 2 or more carbon atoms is not particularly limited. For example, an alkyl group having 2 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms containing a heteroatom in the chain can be cited.

[0548] As the alkyl group having 2 to 20 carbon atoms containing a heteroatom in the chain, for example, an alkyl group in which one or two or more -CH2- are substituted with a divalent organic group such as -O-, -S-, -CO-, -NR6- or a combination of two or more of them can be cited. The above R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0549] Specific examples of the non-acid-decomposable alkyl group that may contain a heteroatom in the chain and has 2 or more carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethylpentyl, 2-ethylhexyl, and an alkyl group in which one or two or more -CH2- are substituted with -O- or -O-CO-.

[0550] The number of carbon atoms of the non-acid-decomposable alkyl group that may contain a heteroatom in the chain and has 2 or more carbon atoms is preferably 2 or more and 16 or less, more preferably 2 or more and 10 or less, and still more preferably 2 or more and 8 or less. The lower limit of the number of carbon atoms of the non-acid-decomposable alkyl group having 2 or more carbon atoms is preferably 4 or more.

[0551] In addition, the non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (for example, substituent T).

[0552] The repeating unit (al) is preferably a repeating unit represented by the following general formula (1-2).

[0553] [Chemical formula 37]

[0554]

[0555] In the general formula (1-2), R1 represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. R2 represents a non-acid-decomposable alkyl group that may contain a heteroatom in the chain and has 2 or more carbon atoms.

[0556] The halogen atom represented by R1 is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0557] The alkyl group represented by R1 is not particularly limited, and examples thereof include alkyl groups having 1 to 10 carbon atoms. Specifically, examples thereof include a methyl group, an ethyl group, and a tert-butyl group. Among them, an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred.

[0558] The cycloalkyl group represented by R1 is not particularly limited, and examples thereof include cycloalkyl groups having 5 to 10 carbon atoms. More specifically, examples thereof include a cyclohexyl group.

[0559] As R1, a hydrogen atom or a methyl group is preferred.

[0560] The definition and preferred mode of the non-acid-decomposable alkyl group represented by R2, which may contain a heteroatom in the chain and has 2 or more carbon atoms, are as described above.

[0561] Furthermore, from the viewpoint of being able to more easily volatilize the residual solvent, the repeating unit (a1) may be a repeating unit having a non-acid-decomposable alkyl group that may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group that may contain a heteroatom in the ring member and has a carboxyl group or a hydroxyl group.

[0562] Hereinafter, a repeating unit having a non-acid-decomposable alkyl group that may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group that may contain a heteroatom in the ring member and has a carboxyl group or a hydroxyl group will be described.

[0563] The non-acid-decomposable alkyl group may be either linear or branched.

[0564] The non-acid-decomposable alkyl group preferably has 2 or more carbon atoms. From the viewpoint of setting the Tg of the homopolymer to 50 °C or lower, the upper limit of the number of carbon atoms of the non-acid-decomposable alkyl group is, for example, preferably 20 or lower.

[0565] The non-acid-decomposable alkyl group that may contain a heteroatom in the chain is not particularly limited. For example, it includes 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 above alkyl group is substituted with a carboxyl group or a hydroxyl group.

[0566] Examples of the alkyl group having 2 to 20 carbon atoms containing a heteroatom in the chain include an alkyl group in which one or two or more -CH2- are substituted with a divalent organic group such as -O-, -S-, -CO-, -NR6- or a combination of two or more of them. The above R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0567] Regarding the number of carbon atoms of the non-acid-decomposable alkyl group that can contain a heteroatom in the chain, from the viewpoint of more excellent crack resistance (less likely to generate cracks), it is preferably 2 to 16, more preferably 2 to 10, and further preferably 2 to 8.

[0568] In addition, the non-acid-decomposable alkyl group may have a substituent (for example, substituent T).

[0569] As a specific example of the repeating unit having a non-acid-decomposable alkyl group containing a heteroatom in the chain and having a carboxyl group, for example, a repeating unit having the following structure can be cited.

[0570] [Chemical formula 38]

[0571]

[0572] 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 lower, the upper limit of the number of carbon atoms of the above non-acid-decomposable cycloalkyl group is preferably 20 or lower, more preferably 16 or lower, and further preferably 10 or lower.

[0573] The non-acid-decomposable cycloalkyl group that can contain a heteroatom in the ring member is not particularly limited. For example, a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group) and a cycloalkyl group having 5 to 20 carbon atoms containing a heteroatom in the ring member can be cited. In addition, at least one of the hydrogen atoms in the above cycloalkyl group is substituted with a carboxyl group or a hydroxyl group.

[0574] As the cycloalkyl group having 5 to 20 carbon atoms containing a heteroatom in the ring member, for example, a cycloalkyl group in which one or two or more -CH2- are substituted with a divalent organic group such as -O-, -S-, -CO-, -NR6- or a combination of two or more thereof can be cited. The above R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0575] In addition, the non-acid-decomposable cycloalkyl group may have a substituent (for example, substituent T).

[0576] As the repeating unit having a non-acid-decomposable alkyl group that can contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group or a non-acid-decomposable cycloalkyl group that can contain a heteroatom in the ring member and has a carboxyl group or a hydroxyl group, from the viewpoint of more excellent effects of the present invention, among them, a repeating unit represented by the following general formula (1-3) is preferred.

[0577] [Chemical formula 39]

[0578]

[0579] In 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 that may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group that may contain a heteroatom in the ring members and has a carboxyl group or a hydroxyl group.

[0580] In General Formula (1-3), R3 has the same meaning as R1 described above, and the preferred modes are also the same.

[0581] The definition and preferred modes of the non-acid-decomposable alkyl group that may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or the non-acid-decomposable cycloalkyl group that may contain a heteroatom in the ring members and has a carboxyl group or a hydroxyl group, represented by R4, are as described above.

[0582] Among them, as R4, a non-acid-decomposable cycloalkyl group that may contain a heteroatom in the ring members and has a carboxyl group or a hydroxyl group is preferred. As such a mode, for example, repeating units having the following structures can be cited.

[0583] [Chemical Formula 40]

[0584]

[0585] As the monomer a1, for example, ethyl acrylate (-22 °C), n-propyl acrylate (-37 °C), isopropyl acrylate (-5 °C), n-butyl acrylate (-55 °C), n-butyl methacrylate (20 °C), n-hexyl acrylate (-57 °C), n-hexyl methacrylate (-5 °C), n-octyl methacrylate (-20 °C), 2-ethylhexyl acrylate (-70 °C), isononyl acrylate (-82 °C), lauryl methacrylate (-65 °C), 2-hydroxyethyl acrylate (-15 °C), 2-hydroxypropyl methacrylate (26 °C), 1-[2-(methacryloyloxy)ethyl] succinate (9 °C), 2-ethylhexyl methacrylate (-10 °C), sec-butyl acrylate (-26 °C), methoxypolyethylene glycol monomethyl acrylate (n = 2) (-20 °C), cetyl acrylate (35 °C), etc. are cited. In addition, the value in parentheses represents the Tg (°C) when a homopolymer is formed.

[0586] In addition, methoxypolyethylene glycol monomethyl acrylate (n = 2) is a compound having the following structure.

[0587] [Chemical Formula 41]

[0588]

[0589] The monomer a1 is preferably n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, cetyl acrylate, 2-hydroxyethyl acrylate, and the compound represented by the following MA-5.

[0590] [Chemical formula 42]

[0591]

[0592] The resin (A) may contain only one kind of repeating unit (a1), or may contain two or more kinds.

[0593] In the resin (A), the content of the repeating unit (a1) (the total when there are a plurality of repeating units (a1)) 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 when there are a plurality of repeating units (a1)) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, and further preferably 5 to 30 mol%, relative to all the repeating units of the resin (A).

[0594] (Repeating unit (a4) having a phenolic hydroxyl group)

[0595] The resin (A) may contain a repeating unit (a4) having a phenolic hydroxyl group.

[0596] By containing the repeating unit (a4), the resin (A) has a more excellent dissolution rate during alkali development and excellent etching resistance.

[0597] The repeating unit having a phenolic hydroxyl group is not particularly limited, and examples thereof include a hydroxystyrene repeating unit or 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).

[0598] [Chemical formula 43]

[0599]

[0600] In the formula,

[0601] R 41 , R 42 and R 43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R 42 may be bonded to Ar4 to form a ring, and in this case, R 42 represents a single bond or an alkylene group.

[0602] X4 represents a single bond, -COO-, or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group.

[0603] L4 represents a single bond or a divalent linking group.

[0604] Ar4 represents an (n + 1)-valent aromatic hydrocarbon group, and when it forms a ring by bonding with R 42 it represents an (n + 2)-valent aromatic hydrocarbon group.

[0605] n represents an integer from 1 to 5.

[0606] In order to highly polarize the repeating unit represented by the general formula (I), it is also preferred that n is an integer of 2 or more, or X4 is -COO- or -CONR 64 -.

[0607] As the alkyl group represented by R 41 , R 42 and R 43 in the general formula (I), alkyl groups having 20 or fewer carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, which may have substituents, are preferred, alkyl groups having 8 or fewer carbon atoms are more preferred, and alkyl groups having 3 or fewer carbon atoms are further preferred.

[0608] As the cycloalkyl group represented by R 41 , R 42 and R 43 in the general formula (I), it can be a monocyclic or polycyclic cycloalkyl group. Monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl, which may have substituents, are preferred.

[0609] As the halogen atom represented by R 41 , R 42 and R 43 in the general formula (I), fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be cited, and fluorine atom is preferred.

[0610] As the alkyl group contained in the alkoxycarbonyl group represented by R 41 , R 42 and R 43 in the general formula (I), an alkyl group preferably the same as the alkyl groups in the above R 41 , R 42 and R 43 is preferred.

[0611] As preferred substituents in the above-mentioned groups, for example, alkyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxy, carboxy, halogen atom, alkoxy, thioether, acyl, acyloxy, alkoxycarbonyl, cyano, nitro, etc. may be mentioned. The number of carbon atoms of the substituent is preferably 8 or less.

[0612] Ar4 represents an (n + 1)-valent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group when n is 1 may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms such as phenylene, tolylene group, naphthylene, anthrylene, etc., or an aromatic hydrocarbon group containing a heterocycle such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, etc.

[0613] As a specific example of the (n + 1)-valent aromatic hydrocarbon group when n is an integer of 2 or more, a group formed by removing (n - 1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic hydrocarbon group can be preferably selected.

[0614] The (n + 1)-valent aromatic hydrocarbon group may further have a substituent.

[0615] As substituents that the above-mentioned alkyl, cycloalkyl, alkoxycarbonyl, and (n + 1)-valent aromatic hydrocarbon group may have, for example, the alkyl groups exemplified for R 41 、R 42 and R 43 in the general formula (I); alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl; etc.

[0616] As the -CONR 64 -(R 64 represents a hydrogen atom or an alkyl group) represented by X4, the alkyl group of R 64 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 that may have a substituent, and more preferably an alkyl group having 8 or less carbon atoms.

[0617] As X4, a single bond, -COO-, or -CONH- is preferred, and a single bond or -COO- is more preferred.

[0618] As the divalent linking group of L4, an alkylene group is preferred, and as the alkylene group, an alkylene group having 1 to 8 carbon atoms such as methylene, vinyl, propylene, butylene, hexylene, and octylene that may have a substituent is preferred.

[0619] As Ar4, it is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have substituents, more preferably a phenyl group, a naphthyl group or a biphenylenyl group. Among them, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar4 is preferably a phenyl group.

[0620] Specific examples of the repeating unit having a phenolic hydroxyl group are shown below, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

[0621] [Chemical formula 44]

[0622]

[0623] The resin (A) preferably has a phenolic hydroxyl group.

[0624] The resin (A) may have one kind of repeating unit (a4) alone, or may have two or more kinds in combination.

[0625] 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). Also, the content of the repeating unit (a4) is preferably 85 mol% or less, more preferably 80 mol% or less, relative to all the repeating units in the resin (A).

[0626] In addition to having the above structural units, the resin (A) can have various structural units for the purpose of adjusting dry etching resistance, adaptability to a standard developer, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general necessary properties as a resist. As such structural units, structural units corresponding to other monomers can be cited, but it is not limited to these.

[0627] As other monomers, for example, compounds having one addition-polymerizable unsaturated bond selected from acrylate esters, methacrylate esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. can be cited.

[0628] In addition to these, as long as it is an addition-polymerizable unsaturated compound capable of copolymerizing with the monomers corresponding to the above various structural units, it can also be copolymerized.

[0629] In the resin (A), the molar ratio of the content of each structural unit is appropriately set in order to adjust various properties.

[0630] When the photosensitive radiation-curable or radiation-sensitive resin composition according to the present invention is used for ArF laser exposure, from the viewpoint of the transparency of ArF light, it is preferred that the resin (A) substantially does not have an aromatic group. More specifically, among all the structural units of the resin (A), the structural units having an aromatic group are preferably 5 mol% or less of the whole, more preferably 3 mol% or less, and further preferably ideally 0 mol%, that is, the structural units having an aromatic group are not contained. Further, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0631] It is preferred that all the structural units of the resin (A) are composed of (meth)acrylate-based structural units. In this case, any one of a resin having all methacrylate-based structural units, a resin having all acrylate-based structural units, and a resin having structural units formed of both methacrylate-based structural units and acrylate-based structural units can be used, but it is preferred that the acrylate-based structural units are 50 mol% or less of all the structural units of the resin (A).

[0632] When the photosensitive radiation-curable or radiation-sensitive resin composition according to the present invention is used for KrF exposure, electron beam (EB) exposure, or extreme ultraviolet (EUV) exposure, the resin (A) preferably contains a structural unit having an aromatic hydrocarbon group. The resin (A) more preferably contains a structural unit having a phenolic hydroxyl group.

[0633] As the structural unit having a phenolic hydroxyl group, for example, the above repeating unit (a4) can be cited.

[0634] When the photosensitive radiation-curable or radiation-sensitive resin composition according to the present invention is used for KrF exposure, EB exposure, or EUV exposure, the resin (A) preferably has a structure in which a hydrogen atom of the phenolic hydroxyl group is protected by a group (leaving group) that is decomposed and detached by the action of an acid.

[0635] The content of the structural unit having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and further preferably 50 mol% to 100 mol% with respect to all the structural units in the resin (A).

[0636] The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, further preferably 3,000 to 15,000, and particularly preferably 3,000 to 11,000.

[0637] The dispersity (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, further preferably 1.0 to 2.0, and particularly preferably 1.1 to 2.0.

[0638] Specific examples of the resin (A) include resins A-1 to A-12 used in the examples, but are not limited thereto.

[0639] The resin (A) may be used alone or in combination of two or more.

[0640] The content of the resin (A) is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 60% by mass or more, and particularly preferably 80% by mass or more, based on the total solid content of the radiation-sensitive or radiation-sensitive resin composition according to the present invention. The upper limit is not particularly limited, and is preferably 99.5% by mass or less, more preferably 99% by mass or less, and still more preferably 97% by mass or less.

[0641] 〔Hydrophobic resin〕

[0642] The radiation-sensitive or radiation-sensitive resin composition according to the present invention preferably also contains a hydrophobic resin (also referred to as "hydrophobic resin (E)").

[0643] The radiation-sensitive or radiation-sensitive resin composition according to the present invention preferably contains at least a hydrophobic resin (E) other than a resin whose polarity is increased by the action of an acid and a resin whose polarity is increased by the action of an acid.

[0644] Since the radiation-sensitive or radiation-sensitive resin composition according to the present invention contains the hydrophobic resin (E), it is possible to control the static / dynamic contact angle on the surface of the radiation-sensitive or radiation-sensitive film. Thereby, it is possible to improve the development characteristics, suppress degassing, improve the immersion liquid followability in liquid immersion exposure, and reduce liquid immersion defects.

[0645] The hydrophobic resin (E) is preferably designed to be biased toward the surface of the resist film. However, unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule, and may not contribute to the uniform mixing of polar / non-polar substances.

[0646] In the present invention, a resin having a fluorine atom is treated as a hydrophobic resin and a fluorine-containing resin described later. And a resin containing a structural unit having the above acid-decomposable group preferably does not have a fluorine atom.

[0647] From the viewpoint of being biased toward the film surface layer, the hydrophobic resin (E) is preferably a resin containing a structural unit having at least one selected from "fluorine atom", "silicon atom", and "CH3 partial structure contained in the side chain portion of the resin".

[0648] When the hydrophobic resin (E) contains a fluorine atom or a silicon atom, the above fluorine atom or silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin or in the side chain.

[0649] The hydrophobic resin (E) preferably has at least one group selected from the group consisting of the following (x) to (z).

[0650] (x) Acid group

[0651] (y) A group that decomposes by the action of an alkaline developer and increases its solubility in the alkaline developer (hereinafter, also referred to as a polarity-converting group).

[0652] (z) A group that decomposes by the action of an acid

[0653] Examples of the acid group (x) include phenolic hydroxyl group, carboxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfimide group, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene, and tris(alkylsulfonyl)methylene, etc.

[0654] As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol group), sulfimide group, or bis(alkylcarbonyl)methylene is preferred.

[0655] Examples of the group (y) that decomposes by the action of an alkaline developer and increases its solubility in the alkaline developer include lactone group, carboxylic acid ester group (-COO-), acid anhydride group (-C(O)OC(O)-), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO2O-), and sulfonic acid ester group (-SO2O-), etc. A lactone group or carboxylic acid ester group (-COO-) is preferred.

[0656] The structural unit containing these groups is a structural unit in which these groups are directly bonded to the main chain of the resin. Examples include structural units based on acrylate and methacrylate. This structural unit can bond these groups to the main chain of the resin via a linking group. Alternatively, this structural unit can be used when polymerizing a polymerization initiator or chain transfer agent having these groups and introduced into the terminal of the resin.

[0657] Examples of the structural unit having a lactone group include the same repeating units as the structural units having a lactone structure described in the item of the previous resin (A).

[0658] The content of the structural unit having the group (y) that decomposes by the action of an alkaline developer and increases its solubility in the 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 structural units in the hydrophobic resin (E).

[0659] Examples of the structural unit having a group (z) decomposable by the action of an acid in the hydrophobic resin (E) include the same repeating units as the structural units having an acid-decomposable group exemplified in the resin (A). The structural unit having a group (z) decomposable by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the structural unit having a group (z) decomposable by the action of an acid is preferably 1 mol% to 80 mol%, more preferably 10 mol% to 80 mol%, and still more preferably 20 mol% to 60 mol% with respect to all the structural units in the resin (E).

[0660] The hydrophobic resin (E) may further have a structural unit different from the above structural unit.

[0661] The structural unit containing a fluorine atom is preferably 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol% with respect to all the structural units contained in the hydrophobic resin (E). Further, the structural unit containing a silicon atom is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol% with respect to all the structural units contained in the hydrophobic resin (E).

[0662] On the other hand, particularly when the hydrophobic resin (E) contains a CH3 partial structure in the side chain portion, the hydrophobic resin (E) is also preferably in a form substantially free of fluorine atoms and silicon atoms. Further, the hydrophobic resin (E) is preferably composed essentially of structural units composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

[0663] The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.

[0664] The total content of the residual monomer and oligomer components contained in the hydrophobic resin (E) is preferably 0.01 mass% to 5 mass%, more preferably 0.01 mass% to 3 mass%. Further, the dispersity (Mw / Mn) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.

[0665] As the hydrophobic resin (E), known resins can be appropriately selected and used alone or as a mixture thereof. For example, the known resins disclosed in paragraphs 0451 to 0704 of the specification of US Patent Application Publication No. 2015 / 0168830 and paragraphs 0340 to 0356 of the specification of US Patent Application Publication No. 2016 / 0274458 can be preferably used as the hydrophobic resin (E). Further, the structural units disclosed in paragraphs 0177 to 0258 of the specification of US Patent Application Publication No. 2016 / 0237190 are also preferably used as the structural units constituting the hydrophobic resin (E).

[0666] -Fluororesin-

[0667] The hydrophobic resin (E) is preferably a resin containing fluorine atoms (also referred to as "fluororesin").

[0668] When the hydrophobic resin (E) contains fluorine atoms, as the partial structure having fluorine atoms, a resin containing an alkyl group having fluorine atoms, a cycloalkyl group having fluorine atoms, or an aryl group having fluorine atoms is preferred.

[0669] The alkyl group having fluorine atoms is a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms.

[0670] The cycloalkyl group having fluorine atoms is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is replaced by a fluorine atom.

[0671] As the aryl group having fluorine atoms, a group in which at least one hydrogen atom in an aryl group such as a phenyl group and a naphthyl group is replaced by a fluorine atom can be mentioned.

[0672] As the alkyl group having fluorine atoms, the cycloalkyl group having fluorine atoms, and the aryl group having fluorine atoms, groups represented by Formulas F2 to F4 are preferred.

[0673] [Chemical formula 45]

[0674]

[0675] In Formulas F2 to F4,

[0676] R 57 ~R 68 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group (linear or branched). Among them, at least one of R 57 ~R 61 , at least one of R 62 ~R 64 , and at least one of R 65 ~R 68 each independently represents a fluorine atom or an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom.

[0677] R 57 ~R 61 and R 65 ~R 67 are preferably all fluorine atoms. R 62 , R 63 and R 68 are preferably an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom (preferably having 1 to 4 carbon atoms), more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R 62 and R63 They can be bonded to each other to form a ring.

[0678] Among them, from the viewpoint of more excellent effects involved in the present invention, the fluororesin preferably has alkali decomposability.

[0679] The so-called fluororesin having alkali decomposability means that 100 mg of the fluororesin is added to a mixed solution of 2 mL of a buffer solution with a pH of 10 and 8 mL of THF, allowed to stand at 40 °C, and hydrolysis occurs in an amount of 30 mol% or more of the total amount of decomposable groups in the fluororesin after 10 minutes. In addition, the decomposition rate can be calculated from the ratio of the raw material to the decomposition product obtained by NMR analysis.

[0680] From the viewpoints of the tolerance of the depth of focus, pattern linearity, improvement of the development characteristics, suppression of outgassing, improvement of the immersion liquid followability in immersion lithography, and reduction of immersion defects, the fluororesin preferably has a structural unit represented by formula X.

[0681] Moreover, from the viewpoints of the tolerance of the depth of focus, pattern linearity, improvement of the development characteristics, suppression of outgassing, improvement of the immersion liquid followability in immersion lithography, and reduction of immersion defects, the photosensitive radiation-sensitive or radiation-sensitive resin composition according to the present invention preferably further contains a fluororesin having a structural unit represented by formula X.

[0682] [Chemical formula 46]

[0683]

[0684] In formula X, Z represents a halogen atom, a group represented by R 11 OCH2-, or a group represented by R 12 OC(=0)CH2-, R 11 and R 12 each independently represent a substituent, and X represents an oxygen atom or a sulfur atom. L represents an (n + 1)-valent linking group, R 10 represents a group having a group that decomposes by the action of an alkaline aqueous solution and increases the solubility of the fluororesin in the alkaline aqueous solution, n represents a positive integer, and when n is 2 or more, a plurality of R 10 may be the same as or different from each other.

[0685] Examples of the halogen atom as Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

[0686] Examples of the substituents of R 11 and R 12 include an alkyl group (preferably having 1 to 4 carbon atoms), a cycloalkyl group (preferably having 6 to 10 carbon atoms), and an aryl group (preferably having 6 to 10 carbon atoms). Moreover, as R 11 and R12 The substituent may further have a substituent. As such a further substituent, an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (preferably having 1 to 4 carbon atoms), and a carboxyl group can be mentioned.

[0687] The linking group for L is preferably a divalent or trivalent linking group (in other words, n is preferably 1 or 2), more preferably a divalent linking group (in other words, n is preferably 1). The linking group for L is preferably a linking group selected from the group consisting of an aliphatic group, an aromatic group, and a combination thereof.

[0688] For example, when n is 1 and the linking group for L is a divalent linking group, as the divalent aliphatic group, an alkylene group, an alkenylene group, an alkynylene group, or a polyalkyleneoxy group can be mentioned. Among them, an alkylene group or an alkenylene group is preferred, and an alkylene group is more preferred.

[0689] The divalent aliphatic group may have a chain structure or a cyclic structure, but compared with the cyclic structure, a chain structure is preferred, and compared with a branched chain structure, a straight-chain structure is preferred. The divalent aliphatic group may have a substituent. As the substituent, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group can be mentioned.

[0690] As the divalent aromatic group, an arylene group can be mentioned. Among them, a phenylene group and a naphthylene group are preferred.

[0691] The divalent aromatic group may have a substituent. In addition to the examples of the substituents in the above-mentioned divalent aliphatic group, an alkyl group can also be mentioned.

[0692] Moreover, as L, it can be a divalent group obtained by removing two hydrogen atoms at arbitrary positions from the structures represented by the above formulas LC1-1 to LC1-21 or formulas SL1-1 to SL-3.

[0693] When n is 2 or more, as a specific example of the (n + 1)-valent linking group, a group formed by removing any (n - 1) hydrogen atoms from the specific examples of the above divalent linking group can be mentioned.

[0694] As specific examples of L, for example, the following linking groups can be mentioned.

[0695] [Chemical formula 47]

[0696] -CH2- -CH2CH2- -CH2cH2cH2- -cH2CH2CH2CH2-

[0697] -CH2CH2CH2CH2CH2- -CH2CH2CH2CH2CH2CH2-

[0698]

[0699] In addition, these linking groups may further have substituents as described above.

[0700] As R 10 , it is preferably a group represented by the following formula W.

[0701] -Y-R 20 Formula W

[0702] In the above formula W, Y represents a group that decomposes by the action of an alkaline aqueous solution and has an increased solubility in the alkaline aqueous solution. R 20 represents an electron-withdrawing group.

[0703] Examples of Y include a carboxylic acid ester group (-COO- or OCO-), an acid 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-), and a carboxylic acid ester group is preferred.

[0704] As the above electron-withdrawing group, it is preferably a partial structure represented by the following formula EW. The * in formula EW represents a bonding bond directly bonded to the group Y in formula W.

[0705] [Chemical formula 48]

[0706]

[0707] In formula EW,

[0708] n ew is the repetition number of the linking group represented by -C(R ew1 )(R ew2 ), and represents an integer of 0 or 1. When n ew is 0, it represents a single bond, indicating that Y ew1 is directly bonded.

[0709] Y ew1 may include a halogen atom, a cyano group, a nitro group, a halo(cyclo)alkyl group, a haloaryl group, an oxy group, a carbonyl group, a sulfonyl group, a sulfinyl group, and a combination thereof represented by -C(R f1 )(R f2 )-R f3 . (Wherein, when Y ew1 is a halogen atom, a cyano group or a nitro group, n ew is 1.)

[0710] R ew1 and R ew2 each independently represents an arbitrary group, for example, a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), or an aryl group (preferably having 6 to 10 carbon atoms).

[0711] R ew1 , R ew2 and Y ew1 at least two of them can be connected to each other to form a ring.

[0712] In addition, "halo(cyclo)alkyl" represents at least partially halogenated alkyl and cycloalkyl, and "haloaryl" represents at least partially halogenated aryl.

[0713] As Y ew1 , it is preferably a halogen atom, a halo(cyclo)alkyl or haloaryl represented by -C(R f1 )(R f2 )-R f3 .

[0714] R f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group or a perhaloaryl group, preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoromethyl group.

[0715] R f2 and R f3 each independently represents a hydrogen atom, a halogen atom or an organic group, and R f2 and R f3 can be connected to form a ring. As the organic group, an alkyl group, a cycloalkyl group and an alkoxy group can be mentioned, and they can be substituted by a halogen atom (preferably a fluorine atom). R f2 and R f3 are preferably (halo)alkyl or (halo)cycloalkyl. R f2 is more preferably the same group as R f1 , or forms a ring by connecting with R f3 .

[0716] As the ring formed by the connection of R f2 and R f3 , a (halo)cycloalkyl ring can be mentioned.

[0717] As the (halo)alkyl in R f1 to R f3 , it can be either linear or branched. As the linear (halo)alkyl, it preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.

[0718] As the or R in R f1 to R f3 inf2 The (halo)cycloalkyl group in the ring formed by connecting with R f3 can be monocyclic or polycyclic. In the case of polycyclic, the (halo)cycloalkyl group can be bridged. That is, in this case, the (halo)cycloalkyl group can have a bridging structure.

[0719] Examples of such (halo)cycloalkyl groups include the groups represented by the following formulae and their halogenated groups. In addition, a part of the carbon atoms in the cycloalkyl group can be substituted by heteroatoms such as oxygen atoms.

[0720] [Chemical formula 49]

[0721]

[0722] As R f2 and R f3 in or R f2 connected to R f3 to form the (halo)cycloalkyl group in the ring, it is preferably a fluorocycloalkyl group represented by -C (n) F (2n-2) H. Here, the number of carbon atoms n is not particularly limited, preferably 5 to 13, more preferably 6.

[0723] Y ew1 in or R f1 in the (per)haloaryl group, examples include perfluoroaryl groups represented by -C (n) F (n-1) Here, the number of carbon atoms n is not particularly limited, preferably 5 to 13, more preferably 6.

[0724] As R ew1 、R ew2 and Y ew1 in, at least two of them can be connected to each other to form a ring, preferably a cycloalkyl group or a heterocyclic group.

[0725] Each group and each ring constituting the partial structure represented by the above formula EW can further have substituents.

[0726] In the above formula W, R 20 is preferably an alkyl group substituted by one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group, more preferably an alkyl group substituted by a halogen atom (haloalkyl group), and still more preferably a fluoroalkyl group. The number of carbon atoms of the alkyl group substituted by one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group is preferably 1 to 10, more preferably 1 to 5.

[0727] More specifically, R 20 is preferably -C(R’ 1 )(R’ f1 )(R’f2 ) or -C(R’ 1 )(R’ 2 )(R’ f1 ), where the group represented by R’ 1 and R’ 2 each independently represents a hydrogen atom or an alkyl group which is not substituted by an electron-withdrawing group (preferably unsubstituted). R’ f1 and R’ f2 each independently represents a halogen atom, a cyano group, a nitro group or a perfluoroalkyl group.

[0728] As R’ 1 and R’ 2 the alkyl group can be linear or branched, preferably having 1 to 6 carbon atoms.

[0729] As R’ f1 and R’ f2 the perfluoroalkyl group can be linear or branched, preferably having 1 to 6 carbon atoms.

[0730] As a preferred specific example of R 20 , -CF3, -C2F5, -C3F7, -C4F9, -CF(CF3)2, -CF(CF3)C2F5, -CF2CF(CF3)2, -C(CF3)3, -C5F 11 , -C6F 13 , -C7F 15 , -C8F 17 , -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, -CH(CF3)C2F5, -CH2CF(CF3)2 and -CH2CN can be cited. Among them, -CF3, -C2F5, -C3F7, -C4F9, -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2 or -CH2CN are preferred, -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2 or -CH2CN are more preferred, -CH2C2F5, -CH(CF3)2 or -CH2CN are further preferred, and -CH2C2F5 or -CH(CF3)2 are particularly preferred.

[0731] As the structural unit represented by formula X, the structural unit represented by the following formula X-1 or formula X-2 is preferred, and the structural unit represented by formula X-1 is more preferred.

[0732] [Chemical formula 50]

[0733]

[0734] In formula X-1, R20 represents an electron-withdrawing group, L 2 represents a divalent linking group, X 2 represents an oxygen atom or a sulfur atom, Z 2 represents a halogen atom.

[0735] In formula X-2, R 20 represents an electron-withdrawing group, L 3 represents a divalent linking group, X 3 represents an oxygen atom or a sulfur atom, Z 3 represents a halogen atom.

[0736] As L 2 and L 3 Specific examples and preferred examples of the divalent linking group are the same as those described for L as the divalent linking group in the above formula X.

[0737] As R 2 and R 3 The electron-withdrawing group is preferably a partial structure represented by the above formula EW, and specific examples and preferred examples are also as described above, and more preferably a halo(cyclo)alkyl group.

[0738] In the above formula X-1, L 2 and R 2 do not bond to each other to form a ring. In the above formula X-2, L 3 and R 3 do not bond to each other to form a ring.

[0739] As X 2 and X 3 , preferably an oxygen atom.

[0740] As Z 2 and Z 3 , preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.

[0741] Moreover, as the structural unit represented by formula X, the structural unit represented by formula X-3 is also preferred.

[0742] [Chemical formula 51]

[0743]

[0744] In formula X-3, R 20 represents an electron-withdrawing group, R 21 represents a hydrogen atom, an alkyl group or an aryl group, L 4 represents a divalent linking group, X 4 represents an oxygen atom or a sulfur atom, and m represents 0 or 1.

[0745] As L 4Specific examples and preferred examples of the divalent linking group are the same as those described for L as the divalent linking group in Formula X.

[0746] As R 4 The electron-withdrawing group is preferably a partial structure represented by the above Formula EW, and specific examples and preferred examples are also as described above, and more preferably a halo(cyclo)alkyl group.

[0747] Further, in the above Formula X-3, L 4 and R 4 do not bond to each other to form a ring.

[0748] As X 4 is preferably an oxygen atom.

[0749] Moreover, as the structural unit represented by Formula X, a structural unit represented by Formula Y-1 or a structural unit represented by Formula Y-2 is also preferred.

[0750] [Chemical formula 52]

[0751]

[0752] In Formula Y-1 and Formula Y-2, Z represents a halogen atom, a group represented by R 11 OCH2-, or a group represented by R 12 OC(=O)CH2-, R 11 and R 12 each independently represent a substituent, and R 20 represents an electron-withdrawing group.

[0753] As R 20 The electron-withdrawing group is preferably a partial structure represented by the above Formula EW, and specific examples and preferred examples are also as described above, and more preferably a halo(cyclo)alkyl group.

[0754] Specific examples and preferred examples of the halogen atom, the group represented by R 11 OCH2-, and the group represented by R 12 OC(=O)CH2- as Z are the same as those described in the above Formula 1.

[0755] The content of the structural unit represented by Formula X is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol%, and further preferably 30 mol% to 100 mol% relative to all the structural units of the fluororesin.

[0756] Preferred examples of the structural units constituting the hydrophobic resin (E) are shown below.

[0757] As the hydrophobic resin (E), a resin obtained by arbitrarily combining these structural units can be preferably selected, but it is not limited thereto.

[0758] [Chemical formula 53]

[0759]

[0760] [Chemical formula 54]

[0761]

[0762] The hydrophobic resin (E) can be used alone as one kind, or two or more kinds can be used in combination.

[0763] From the viewpoint of achieving both the immersion liquid followability and the developing characteristics in immersion exposure, it is preferable to use two or more hydrophobic resins (E) having different surface energies in combination.

[0764] The content of the hydrophobic resin (E) in the composition is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass, based on the total solid content of the photosensitive actinic or radiation-sensitive resin composition of the present invention.

[0765] <(D) Acid diffusion control agent>

[0766] The photosensitive actinic or radiation-sensitive resin composition of the present invention contains an acid diffusion control agent (also referred to as "acid diffusion control agent (D)").

[0767] As a preferred embodiment, the acid diffusion control agent (D) is preferably an amine compound.

[0768] The acid diffusion control agent (D) captures the acid generated from an acid generator or the like during exposure and functions as a quencher, which suppresses the reaction of the acid-decomposable resin in the unexposed portion due to the excessive generation of acid. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, an onium salt (DC) that is a relatively weak acid with respect to the acid generator, a low-molecular compound (DD) having a nitrogen atom and a group that is detached by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation moiety can be used as the acid diffusion control agent (D).

[0769] Among them, from the viewpoint of the linearity of the pattern obtained over time, the photosensitive actinic or radiation-sensitive resin composition of the present invention preferably contains a nitrogen-containing compound as the acid diffusion control agent (D), and more preferably contains a nitrogen-containing basic compound.

[0770] In the photosensitive radiation - curable or radiation - sensitive resin composition according to the present invention, known acid diffusion control agents can be appropriately used. For example, known compounds disclosed in paragraphs 0627 - 0664 of the specification of U.S. Patent Application Publication No. 2016 / 0070167, paragraphs 0095 - 0187 of the specification of U.S. Patent Application Publication No. 2015 / 0004544, paragraphs 0403 - 0423 of the specification of U.S. Patent Application Publication No. 2016 / 0237190, and paragraphs 0259 - 0328 of the specification of U.S. Patent Application Publication No. 2016 / 0274458 can be preferably used as the acid diffusion control agent (D).

[0771] [Alkaline compound (DA)]

[0772] As the alkaline compound (DA), compounds having structures represented by the following Formula A - Formula E can be preferably selected.

[0773] [Chemical formula 55]

[0774]

[0775] In Formula A and Formula E,

[0776] R 200 , R 201 and R 202 may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 - 20 carbon atoms), a cycloalkyl group (preferably having 3 - 20 carbon atoms), or an aryl group (having 6 - 20 carbon atoms). R 201 and R 202 may be bonded to each other to form a ring.

[0777] R 203 , R 204 , R 205 and R 206 may be the same or different, and each independently represents an alkyl group having 1 - 20 carbon atoms.

[0778] The alkyl groups in Formula A and Formula E may have substituents or may be unsubstituted.

[0779] Regarding the above - mentioned alkyl groups, as the alkyl groups having substituents, aminoalkyl groups having 1 - 20 carbon atoms, hydroxyalkyl groups having 1 - 20 carbon atoms, or cyanoalkyl groups having 1 - 20 carbon atoms are preferred.

[0780] The alkyl groups in Formula A and Formula E are more preferably unsubstituted.

[0781] As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc. are preferred, and compounds having an imidazole structure, a diazabicyclic structure, an oxonium hydroxide structure, a carboxonium structure, a trialkylamine structure, an aniline structure or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, aniline derivatives having a hydroxyl group and / or an ether bond, etc. are more preferred.

[0782] [Basic compound (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation]

[0783] The basic compound (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation (hereinafter, also referred to as "compound (DB)") is a compound having a proton-accepting functional group, and by irradiation with actinic rays or radiation, it decomposes, thereby reducing, disappearing the proton-accepting property or changing from the proton-accepting property to an acidic property.

[0784] The proton-accepting functional group is a group or electron having a functional group capable of electrostatic interaction with a proton. For example, it represents a functional group having a macrocyclic compound structure such as a cyclic polyether, or a functional group having a nitrogen atom as follows, and this nitrogen atom has 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 is, for example, a nitrogen atom having a partial structure represented by the following formula.

[0785] [Chemical formula 56]

[0786] Unshared electron pair

[0787] As a preferred partial structure of the proton-accepting functional group, for example, crown ether, azacrown ether, primary to tertiary amines, pyridine, imidazole and pyrazine structures, etc. can be cited.

[0788] Compound (DB) generates a compound that decomposes by irradiation with actinic rays or radiation, thereby reducing or disappearing the proton-accepting property or changing from the proton-accepting property to an acidic property. Here, the reduction or disappearance of the proton-accepting property or the change from the proton-accepting property to an acidic property is a change in the proton-accepting property caused by the addition of a proton to the proton-accepting functional group. Specifically, it means that when a proton adduct is generated from a compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in this chemical equilibrium decreases.

[0789] The proton-accepting property can be confirmed by performing a pH measurement.

[0790] The acid dissociation constant pKa of the compound generated by the decomposition of compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa < -1, more preferably -13 < pKa < -1, and further preferably -13 < pKa < -3.

[0791] The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution. For example, it is defined in "Kagaku Binran (II)" (Revised 4th Edition, 1993, edited by The Chemical Society of Japan, MARUZEN Co., Ltd.). The lower the value of the acid dissociation constant pKa, the stronger the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be actually measured by measuring the acid dissociation constant at 25 °C using an infinitely diluted aqueous solution. Alternatively, it is also possible to use the following Package 1 and calculate the Hammett substituent constant and the value based on the known literature value database. The pKa values described in this specification all represent the values calculated using this package.

[0792] Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994 - 2007 ACD / Labs).

[0793] ([onium salt (DC) that is relatively a weak acid with respect to the photoacid generator)

[0794] In the photosensitive actinic or radiation-sensitive resin composition according to the present invention, an onium salt (DC) that is relatively a weak acid with respect to the photoacid generator can be used as the acid diffusion control agent (D).

[0795] When an onium salt that generates an acid which is relatively a weak acid with respect to the acid generated from the photoacid generator is mixed and used with the photoacid generator, if the acid generated from the photoacid generator by irradiation with actinic rays or radiation collides with the onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange and an onium salt having a strong acid anion is generated. In this process, the strong acid is exchanged for a weak acid with lower catalytic ability, so the acid is inactivated on the surface and the control of acid diffusion can be carried out.

[0796] From the viewpoints of the depth of focus tolerance and pattern linearity, the photosensitive actinic or radiation-sensitive resin composition according to the present invention preferably further contains at least one compound selected from the group consisting of the compounds represented by Formula d1-1 to Formula d1-3.

[0797] [Chemical Formula 57]

[0798]

[0799] In Formula d1-1 to Formula d1-3, R 51 represents a hydrocarbon group which may have a substituent, Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, provided that a fluorine atom is not bonded to the carbon atom adjacent to the S atom, R 52 represents an organic group, Y 3represents a linear, branched or cyclic alkylene or arylene group, Rf represents a hydrocarbon group containing a fluorine atom, and M + each independently represents an ammonium cation, a sulfonium cation or an iodonium cation.

[0800] As the sulfonium cation or iodonium cation represented by M + preferred examples, there can be mentioned a sulfonium cation exemplified by formula ZI and an iodonium cation exemplified by formula ZII.

[0801] The onium salt (DC) which is a relatively weak acid with respect to the photoacid generator can be a compound having a cationic moiety and an anionic moiety in the same molecule and the cationic moiety and the anionic moiety being covalently bonded (hereinafter, also referred to as "compound (DCA)").

[0802] As the compound (DCA), a compound represented by any one of the following formulas C-1 to C-3 is preferred.

[0803] [Chemical formula 58]

[0804]

[0805] In formulas C-1 to C-3, R 1 , R 2 and R 3 each independently represents a substituent having 1 or more carbon atoms.

[0806] L 1 represents a divalent linking group or a single bond connecting the cationic moiety and the anionic moiety.

[0807] -X - represents an anionic moiety selected from -COO - , -SO3 - , -SO2 - and -N - -R 4 . R 4 represents a monovalent substituent having at least one of a carbonyl (-C(=O)-), a sulfonyl (-S(=O)2-) and a sulfinyl (-S(=O)-) at the linking site with an adjacent N atom.

[0808] R 1 , R 2 , R 3 , R 4 and L 1 can be bonded to each other to form a ring structure. And, in formula C-3, two of R 1 to R 3 are taken together to represent a divalent substituent and can be bonded to the N atom through a double bond.

[0809] As R 1 ~R 3 Examples of the substituent having 1 or more carbon atoms in R include alkyl, cycloalkyl, aryl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, and arylaminocarbonyl. Alkyl, cycloalkyl, or aryl is preferred.

[0810] As the divalent linking group L 1 Examples thereof include linear or branched alkylene, cycloalkylene, arylene, carbonyl, ether bond, ester bond, amide bond, urethane bond, urea bond, and a group formed by combining two or more of these. L 1 Alkylene, arylene, ether bond, ester bond, or a group formed by combining two or more of these is preferred.

[0811] [Low molecular weight compound (DD) having a nitrogen atom and a group that dissociates by the action of an acid]

[0812] The low molecular weight compound (DD) having a nitrogen atom and a group that dissociates by the action of an acid (hereinafter, also referred to as "compound (DD)") is preferably an amine derivative having a group that dissociates by the action of an acid on the nitrogen atom.

[0813] As the group that dissociates by the action of an acid, an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group is preferred, and a urethane group or a hemiaminal ether group is more preferred.

[0814] The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and further preferably 100 to 500.

[0815] The compound (DD) may also have a urethane group having a protecting group on the nitrogen atom. As the protecting group constituting the urethane group, it can be represented by the following formula d-1.

[0816] [Chemical formula 59]

[0817]

[0818] In formula d-1,

[0819] R b each independently represents a hydrogen atom, alkyl (preferably having 1 to 10 carbon atoms), cycloalkyl (preferably having 3 to 30 carbon atoms), aryl (preferably having 3 to 30 carbon atoms), aralkyl (preferably having 1 to 10 carbon atoms), or alkoxyalkyl (preferably having 1 to 10 carbon atoms). R b may be connected to each other to form a ring.

[0820] R bThe alkyl group, cycloalkyl group, aryl group, and aralkyl group represented may each independently be substituted by a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidinyl group, a piperidinyl group, a morpholino group, an oxo group, an alkoxy group, or a halogen atom. For R b The same applies to the alkoxyalkyl group represented.

[0821] As R b , it is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group, more preferably a linear or branched alkyl group or cycloalkyl group.

[0822] As the ring formed by the two Rs b connected to each other, an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon, and derivatives thereof can be cited.

[0823] As the specific structure of the group represented by formula d-1, the structure disclosed in paragraph 0466 of the specification of US Patent Application Publication No. 2012 / 0135348 can be cited, but it is not limited thereto.

[0824] Compound (DD) is preferably a compound having a structure represented by the following formula 6.

[0825] [Chemical formula 60]

[0826]

[0827] In formula 6,

[0828] l represents an integer from 0 to 2, m represents an integer from 1 to 3, and l + m = 3 is satisfied.

[0829] R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Rs a may be the same or different, and the two Rs a may also be connected to each other to form a heterocycle together with the nitrogen atom in the formula. The heterocycle may also contain a heteroatom other than the nitrogen atom in the formula.

[0830] R b has the same meaning as R b in the above formula d-1, and the preferred examples are also the same.

[0831] In formula 6, as the alkyl group, cycloalkyl group, aryl group, and aralkyl group of R a , they may each independently be substituted by the same group as the group described above as the following group, and the group may substitute the alkyl group, cycloalkyl group, aryl group, and aralkyl group of R b .

[0832] As the above R aSpecific examples of the alkyl, cycloalkyl, aryl, and aralkyl groups (which may be substituted by the above groups) may include the same groups as the above specific examples for R b above.

[0833] As a specific structure of the compound (DD) particularly preferred in the present invention, the compound disclosed in paragraph 0475 of the specification of U.S. Patent Application Publication No. 2012 / 0135348 can be cited, but it is not limited thereto.

[0834] The onium salt compound (DE) having a nitrogen atom in the cationic part (hereinafter, also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cationic part. The basic site is preferably an amino group, more preferably an aliphatic amino group. Further preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. And, from the viewpoint of enhancing basicity, it is preferred that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly connected to the nitrogen atom.

[0835] As a preferred specific structure of the compound (DE), the compound disclosed in paragraph 0203 of the specification of U.S. Patent Application Publication No. 2015 / 0309408 can be cited, but it is not limited thereto.

[0836] The following shows preferred examples of the acid diffusion control agent (D), but it is not limited thereto.

[0837] [Chemical formula 61]

[0838]

[0839] [Chemical formula 62]

[0840]

[0841] [Chemical formula 63]

[0842]

[0843] [Chemical formula 64]

[0844]

[0845] [Chemical formula 65]

[0846]

[0847] [Chemical formula 66]

[0848]

[0849] In the photosensitive radiation-curable or radiation-sensitive resin composition according to the present invention, the acid diffusion control agent (D) may be used alone as one kind or two or more kinds may be used in combination.

[0850] The content of the acid diffusion control agent (D) in the composition (the total when there are a plurality of them) is preferably 0.01% by mass to 10% by mass, more preferably 0.02% by mass to 5% by mass based on the total solid content of the composition.

[0851] <Solvent>

[0852] The photosensitive radiation-curable or radiation-sensitive resin composition according to the present invention preferably contains a solvent (also referred to as "solvent (F)"), and more preferably contains an organic solvent.

[0853] In the photosensitive radiation-curable or radiation-sensitive resin composition according to the present invention, known resist solvents can be appropriately used. For example, it is possible to preferably use the solvents disclosed in paragraphs 0665 to 0670 of the specification of US Patent Application Publication No. 2016 / 0070167, paragraphs 0210 to 0235 of the specification of US Patent Application Publication No. 2015 / 0004544, paragraphs 0424 to 0426 of the specification of US Patent Application Publication No. 2016 / 0237190, and paragraphs 0357 to 0366 of the specification of US Patent Application Publication No. 2016 / 0274458.

[0854] Examples of the solvent that can be used in the preparation of the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

[0855] As the organic solvent, a mixed solvent of a solvent containing a hydroxyl group in its structure and a solvent not containing a hydroxyl group can be used.

[0856] As the solvents containing hydroxyl groups and the solvents not containing hydroxyl groups, the above-exemplified compounds can be appropriately selected. However, as the solvents containing hydroxyl groups, alkylene glycol monoalkyl ethers or alkyl lactates are preferred, and propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate are more preferred. And, as the solvents not containing hydroxyl groups, alkylene glycol monoalkyl ether acetates, alkoxypropionic acid alkyl esters, monoketone compounds that may contain a ring, cyclic lactones, or alkyl acetates are preferred, among which, propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane), 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 the solvents not containing hydroxyl groups, propionic acid carbonate esters are also preferred. Among them, from the viewpoint of the uniformity of the formed layer, the solvent particularly preferably contains γ-butyrolactone.

[0857] The mixing ratio (mass ratio) of the solvent containing hydroxyl groups to the solvent not containing hydroxyl groups 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 the solvent not containing hydroxyl groups is preferred.

[0858] The solvent preferably contains propylene glycol monomethyl ether acetate, and can be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

[0859] The solid content concentration of the photosensitive or radiation-sensitive resin composition according to the present invention is not particularly limited, and is preferably 0.5% by mass to 50% by mass, more preferably 1.0% by mass to 45% by mass, and further preferably 1.0% by mass to 40% by mass.

[0860] As a preferred embodiment, the solid content concentration of the above photosensitive or radiation-sensitive resin composition is preferably 10% by mass or more, preferably 15% by mass or more, and preferably 20% by mass or more.

[0861] The solid content concentration is the mass percentage of the mass of other resist components except the solvent with respect to the total mass of the composition.

[0862] <(H) Surfactant>

[0863] The photosensitive or radiation-sensitive resin composition according to the present invention may contain a surfactant (also referred to as "surfactant (H)"), or may not contain it.

[0864] As a preferred embodiment, the radiation-sensitive or radio-sensitive resin composition according to the present invention further contains a surfactant (H). In the case of containing a surfactant, it is preferred to contain at least one of a fluorine-based and a silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom).

[0865] Since the radiation-sensitive or radio-sensitive resin composition according to the present invention contains a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, a resist pattern with less adhesion and development defects can be obtained with good sensitivity and resolution.

[0866] Examples of the fluorine-based or silicon-based surfactant include the surfactants described in paragraph 0276 of US Patent Application Publication No. 2008 / 0248425.

[0867] In addition, other surfactants other than the fluorine-based or silicon-based surfactants described in paragraph 0280 of US Patent Application Publication No. 2008 / 0248425 can also be used.

[0868] These surfactants can be used alone or in combination of two or more.

[0869] When the radiation-sensitive or radio-sensitive resin composition according to the present invention contains a surfactant, the content of the surfactant is preferably 0.0001% by mass to 2% by mass, more preferably 0.0005% by mass to 1% by mass, based on the total solid content of the composition.

[0870] On the other hand, by setting the content of the surfactant to 0.0001% by mass or more based on the total solid content of the composition, the surface distribution unevenness of the hydrophobic resin increases. As a result, the surface of the radiation-sensitive or radio-sensitive film can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[0871] <Other Additives>

[0872] The radiation-sensitive or radio-sensitive resin composition according to the present invention may further contain other known additives.

[0873] Examples of other additives include acid generators, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, dissolution promoters, and the like.

[0874] The photosensitive radiation-curable or radiation-sensitive resin composition of the present invention is preferably prepared by dissolving the above components in a specified organic solvent, preferably the above mixed solvent, filtering it through a filter, and then, for example, coating it on a specified support (substrate) for use.

[0875] The pore size (aperture diameter) of the filter used for filtering is preferably 0.2 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less.

[0876] Moreover, when the solid content concentration of the photosensitive radiation-curable or radiation-sensitive resin composition is high (for example, 25% by mass or more), the pore size of the filter used for filtering is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less.

[0877] The above filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In the filter filtration, as disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-62667, circulation filtration can be performed, or multiple filters can be connected in series or in parallel for filtration. Also, the composition can be filtered multiple times. In addition, a degassing treatment or the like can be performed on the composition before and after the filter filtration.

[0878] <Use>

[0879] The photosensitive radiation-curable or radiation-sensitive resin composition of the present invention is a photosensitive radiation-curable or radiation-sensitive resin composition whose properties change by a light irradiation reaction. More specifically, the photosensitive radiation-curable or radiation-sensitive resin composition of the present invention relates to a photosensitive radiation-curable or radiation-sensitive resin composition of a resist composition for semiconductor manufacturing processes such as IC (Integrated Circuit), manufacturing of circuit boards for liquid crystals or thermal heads, production of imprint mold structures, other photosensitive etching processes, or lithographic printing plates, or production of acid-curable compositions. The resist pattern formed from the photosensitive radiation-curable or radiation-sensitive resin composition of the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring formation processes, and MEMS (MicroElectro Mechanical Systems), etc.

[0880] (Photosensitive radiation-curable or radiation-sensitive film)

[0881] The photosensitive radiation - sensitive or radiation - sensitive film (preferably a resist film) related to the present invention is a film formed from the photosensitive radiation - sensitive or radiation - sensitive resin composition related to the present invention. The photosensitive radiation - sensitive or radiation - sensitive film related to the present invention is a cured product of the photosensitive radiation - sensitive or radiation - sensitive resin composition related to the present invention.

[0882] The cured product in the present invention may be a cured product obtained by removing at least a part of the solvent from the photosensitive radiation - sensitive or radiation - sensitive resin composition related to the present invention.

[0883] Specifically, the photosensitive radiation - sensitive or radiation - sensitive film related to the present invention is obtained by coating the photosensitive radiation - sensitive or radiation - sensitive resin composition related to the present invention on a support such as a substrate and then drying.

[0884] The above - mentioned drying means removing at least a part of the solvent contained in the photosensitive radiation - sensitive or radiation - sensitive resin composition related to the present invention.

[0885] The drying method is not particularly limited, and known methods can be used, such as drying based on heating (for example, 70 °C to 130 °C, 30 seconds to 300 seconds).

[0886] The heating method is not particularly limited, and known heating mechanisms can be used. For example, heaters, ovens, hot plates, infrared lamps, infrared lasers, etc. can be cited.

[0887] The components contained in the photosensitive radiation - sensitive or radiation - sensitive film related to the present invention are the same as the components obtained by removing the solvent from the components contained in the photosensitive radiation - sensitive or radiation - sensitive resin composition related to the present invention, and the preferred modes are also the same.

[0888] The content of each component contained in the photosensitive radiation - sensitive or radiation - sensitive film related to the present invention is equivalent to replacing the description of "total solid content" in the description of the content of each component other than the solvent in the photosensitive radiation - sensitive or radiation - sensitive resin composition related to the present invention with "total mass of the photosensitive radiation - sensitive or radiation - sensitive film".

[0889] The thickness of the photosensitive radiation - sensitive or radiation - sensitive film related to the present invention is not particularly limited, preferably 50 nm to 3000 nm, more preferably 80 nm to 2500 nm.

[0890] Moreover, in the case of forming a thick photosensitive radiation - sensitive or radiation - sensitive film as the storage device is three - dimensionalized, for example, it is preferably 2 μm or more, more preferably 2 μm or more and 50 μm or less, and further preferably 2 μm or more and 20 μm or less.

[0891] Generally, in order to form a thick photosensitive or radiation-sensitive film, there is a tendency to increase the solid content concentration in the photosensitive or radiation-sensitive composition. In such a composition, since components such as resins and photoacid generators can be contained in large amounts, there is a tendency to require more excellent stability over time.

[0892] Since the photosensitive or radiation-sensitive resin composition of the present invention has very excellent stability over time, it can be preferably used in the case of forming a photosensitive or radiation-sensitive film of such a thick film.

[0893] (Pattern formation method)

[0894] The pattern formation method according to the present invention includes:

[0895] A step of exposing the photosensitive or radiation-sensitive film (preferably a resist film) according to the present invention to actinic rays or radiation (exposure step); and

[0896] A step of developing the photosensitive or radiation-sensitive film after the above exposure step using a developer (development step).

[0897] Moreover, the pattern formation method according to the present invention may be a method including the following steps:

[0898] A step of forming a photosensitive or radiation-sensitive film on a support by the photosensitive or radiation-sensitive resin composition according to the present invention (film formation step);

[0899] A step of exposing the photosensitive or radiation-sensitive film to actinic rays or radiation (exposure step); and

[0900] A step of developing the photosensitive or radiation-sensitive film after the above exposure step using a developer (development step).

[0901] <Film formation step>

[0902] The pattern formation method according to the present invention may include a film formation step. As a method for forming the photosensitive or radiation-sensitive film in the film formation step, for example, a method for forming a dry photosensitive or radiation-sensitive film described in the items of the above photosensitive or radiation-sensitive film can be cited.

[0903] 〔Support〕

[0904] The support is not particularly limited, and substrates generally used in other photolithography processes such as photolithography processes for photosensitive etching can be used, except for manufacturing processes of semiconductors such as ICs or manufacturing processes of circuit boards such as liquid crystals or thermal heads. Specific examples of the support include inorganic substrates such as silicon, SiO2, and SiN.

[0905] <Exposure process>

[0906] The exposure process is a process of exposing a photosensitive actinic or radiation-sensitive film to light.

[0907] The exposure method can be immersion exposure.

[0908] The pattern formation method according to the present invention may include multiple exposure processes.

[0909] The type of light (actinic rays or radiation) used for exposure can be selected by considering the characteristics of the photoacid generator and the pattern shape to be obtained, and examples include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams, and far ultraviolet light is preferred.

[0910] For example, actinic rays having a wavelength of 250 nm or less are preferred, more preferably 220 nm or less, and further preferably 1 to 200 nm.

[0911] Specific examples of the light used include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV (13 nm), or electron beams, and ArF excimer laser, EUV, or electron beam is preferred.

[0912] Among them, the exposure in the exposure process is preferably performed by immersion exposure using an ArF excimer laser.

[0913] As the exposure dose, it is preferably 5 mJ / cm 2 ~200 mJ / cm 2 and more preferably 10 mJ / cm 2 ~100 mJ / cm 2 .

[0914] <Development process>

[0915] The developer used in the development process can be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer), and an alkaline aqueous solution is preferred.

[0916] 〔Alkaline developer〕

[0917] As the alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide is preferably used, and in addition, an alkaline aqueous solution such as an inorganic base, a primary to tertiary amine, an alkanolamine, and a cyclic amine can also be used.

[0918] In addition, the above alkaline developer may contain at least one of an appropriate amount of an alcohol and a surfactant. The alkali concentration of the alkaline developer is preferably 0.1% by mass to 20% by mass. The pH of the alkaline developer is preferably 10 to 15.

[0919] The development time using the alkaline developer is preferably 10 seconds to 300 seconds.

[0920] The alkali concentration, pH, and development time of the alkaline developer can be appropriately adjusted according to the formed pattern.

[0921] [Organic developer]

[0922] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent.

[0923] -Ketone solvent-

[0924] As the ketone solvent, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl pentyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonylalcohol, acetylmethanol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate can be cited.

[0925] -Ester solvent-

[0926] As the ester solvent, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, pentyl 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, isoamyl acetate, isobutyl isobutyrate, and butyl propionate can be cited.

[0927] -Other solvents-

[0928] As the alcohol solvent, amide solvent, ether solvent and hydrocarbon solvent, the solvents disclosed in paragraphs 0715 to 0718 of the specification of US Patent Application Publication No. 2016 / 0070167 can be used.

[0929] A plurality of the above solvents can be mixed, or they can be mixed with solvents other than the above or water. As the water content rate of the whole developer, it is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably substantially free of water.

[0930] Relative to the total amount of the developer, the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

[0931] -Surfactant-

[0932] The organic developer can contain an appropriate amount of a known surfactant as needed.

[0933] The content of the surfactant is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 2% by mass, and still more preferably 0.01% by mass to 0.5% by mass relative to the total mass of the developer.

[0934] -Acid diffusion control agent-

[0935] The organic developer can contain the above acid diffusion control agent.

[0936] 〔Developing method〕

[0937] As the developing method, for example, the following methods can be applied: a method (dip method) of immersing a substrate in a tank filled with a developer for a certain period of time; a method (puddle method) of piling up a developer on the substrate surface by surface tension and leaving it for a certain period of time; a method (spray method) of spraying a developer on the substrate surface; or a method (dynamic dispense method) of continuously spraying a developer while scanning a nozzle for spraying a developer at a certain speed on a substrate rotating at a certain speed.

[0938] A step of developing using an alkaline aqueous solution (alkaline developing step) and a step of developing using a developer containing an organic solvent (organic solvent developing step) can also be used in combination. Thus, since pattern formation can be performed without dissolving only the region of the intermediate exposure intensity, a finer pattern can be formed.

[0939] <Preheating process, post-exposure heating process>

[0940] The pattern formation method according to the present invention preferably includes a preheating (PB: PreBake) process before the exposure process.

[0941] The pattern formation method according to the present invention may include multiple preheating processes.

[0942] The pattern formation method according to the present invention preferably includes a post-exposure bake (PEB: Post Exposure Bake) process after the exposure process and before the development process.

[0943] The pattern formation method according to the present invention may include multiple post-exposure heating processes.

[0944] The heating temperature is preferably 70°C to 130°C, more preferably 80°C to 120°C, in any one of the preheating process and the post-exposure heating process.

[0945] The heating time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and further preferably 30 seconds to 90 seconds, in any one of the preheating process and the post-exposure heating process.

[0946] Heating can be performed by the mechanisms provided in the exposure apparatus and the developing apparatus, or a hot plate or the like can be used.

[0947] <Antireflective layer film formation process>

[0948] The pattern formation method according to the present invention may further include a process of forming an antireflective layer film (antireflective layer film formation process) before the film formation process.

[0949] The antireflective layer film formation process is a process of forming an antireflective layer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), antireflective film, etc.) between the resist film and the support. As the antireflective layer film, known organic or inorganic materials can be appropriately used.

[0950] <Protective film formation process>

[0951] The pattern formation method according to the present invention may further include a process of forming a protective film (protective film formation process) before the development process.

[0952] The protective film forming step is a step of forming a protective film (top coat) on the upper layer of the resist film. As the protective film, a known material can be appropriately used. For example, the composition for forming a protective film 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 Publication No. 2016 / 157988 can be preferably used. As the composition for forming a protective film, the above acid diffusion control agent is preferably contained.

[0953] A protective film can be formed on the upper layer of the resist film containing the above hydrophobic resin.

[0954] <Rinsing step>

[0955] The pattern forming method according to the present invention preferably includes a step of cleaning with a rinsing liquid (rinsing step) after the developing step.

[0956] 〔In the case of the developing step using an alkaline developer〕

[0957] In the rinsing step after the developing step using an alkaline developer, for example, pure water can be used as the rinsing liquid. The pure water can contain an appropriate amount of surfactant. In this case, after the developing step or the rinsing step, a treatment of removing the developer or the rinsing liquid adhering to the pattern using a supercritical fluid can be added. In addition, after the rinsing treatment or the treatment using a supercritical fluid, a heat treatment can be performed to remove the moisture remaining in the pattern.

[0958] 〔In the case of the developing step using an organic developer〕

[0959] The rinsing liquid used in the rinsing step after the developing step using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. As the rinsing liquid, a rinsing liquid 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 is preferably used.

[0960] Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent can be the same solvents as those described for the developer containing an organic solvent.

[0961] As the rinsing liquid used in the rinsing step at this time, a rinsing liquid containing a monohydric alcohol is more preferably used.

[0962] As the monohydric alcohol used in the rinsing step, linear, branched or cyclic monohydric alcohols can be cited. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and methyl isobutyl carbinol can be cited. 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 etc. can be cited.

[0963] A plurality of the respective components can be mixed, or they can be used in mixture with organic solvents other than the above.

[0964] The water content rate of the rinsing liquid is preferably 10 mass% or less, more preferably 5 mass% or less, still more preferably 3 mass% or less. By setting the water content rate to 10 mass% or less, favorable development characteristics can be obtained.

[0965] The rinsing liquid can contain an appropriate amount of surfactant.

[0966] In the rinsing step, a rinsing liquid containing an organic solvent is used to perform a cleaning treatment on a substrate developed using an organic developing solution. The method of the cleaning treatment is not particularly limited. For example, a method of continuously ejecting the rinsing liquid onto a substrate rotating at a certain speed (spin coating method), a method of immersing the substrate in a tank filled with the rinsing liquid for a certain time (dipping method), or a method of spraying the rinsing liquid onto the surface of the substrate (spray coating method) etc. can be applied. Among them, it is preferable to perform the cleaning treatment using the spin coating method, and after the cleaning, the substrate is rotated at a rotational speed of 2,000 rpm to 4,000 rpm (revolutions per minute) to remove the rinsing liquid from the substrate. And, it is also preferable to include a heating step (Post Bake) after the rinsing step. By this heating step, the developing solution and the rinsing liquid remaining between and inside the patterns can be removed. In the heating step after the rinsing step, the heating temperature is preferably 40 to 160 °C, more preferably 70 to 95 °C. The heating time is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 90 seconds.

[0967] <Improvement of surface roughness>

[0968] For the pattern formed by the pattern formation method according to 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, a method of treating a resist pattern with plasma of a hydrogen-containing gas, which is disclosed in U.S. Patent Application Publication No. 2015 / 0104957, can be cited. In addition, well-known methods described in, for example, Japanese Patent Application Laid-Open No. 2004-235468, U.S. Patent Application Publication No. 2010 / 0020297, and Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" can be applied.

[0969] Moreover, the resist pattern formed by the above method can be used, for example, as a core material in the spacer process disclosed in Japanese Patent Application Laid-Open No. 3-270227 and U.S. Patent Application Publication No. 2013 / 0209941.

[0970] (Method for manufacturing an electronic device)

[0971] The method for manufacturing an electronic device according to the present invention includes the pattern formation method according to the present invention. The electronic device manufactured by the method for manufacturing an electronic device according to the present invention can be preferably mounted on electrical and electronic devices (for example, home appliances, OA (Office Automation) related devices, media related devices, optical devices, and communication devices, etc.).

[0972] Examples

[0973] Hereinafter, examples are given to further specifically describe the embodiments of the present invention. The materials, amounts used, ratios, treatment contents, treatment steps, etc. shown in the following examples can be appropriately changed within the scope not departing from the gist of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are based on mass.

[0974] <Resin (A)>

[0975] The structures of the resins (A-1 to A-12) used are shown below.

[0976] In addition, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (in terms of polystyrene equivalent). And the composition ratio (molar ratio) of the resin was determined by13 Measured by 13C-NMR (Nuclear Magnetic Resonance).

[0977] [Chemical formula 67]

[0978]

[0979] [Chemical formula 68]

[0980]

[0981] [Chemical formula 69]

[0982]

[0983] In addition, the unit of the content ratio of each repeating unit of the above resin is mol%. t Bu represents tert-butyl, and Et represents ethyl. n Bu represents n-butyl.

[0984] The value of the glass transition temperature (Tg) when monomer a1 is made into a homopolymer can be referred to the description in PCT / JP2018 / 018239. The monomer a1 corresponds to the repeating unit (a1) derived from a monomer whose glass transition temperature (Tg) when made into a homopolymer is 50°C or lower in this specification and the examples.

[0985] <Photoacid generator (B)>

[0986] The structures of the photoacid generators (B-1 to B-16) used are shown below. n Bu represents n-butyl, and tBu represents tert-butyl.

[0987] In addition, the photoacid generators (BX-1 - BX-3) are not photoacid generators (B), but for convenience, they are described below.

[0988] [Chemical formula 70]

[0989]

[0990] [Chemical formula 71]

[0991]

[0992] <Acid diffusion control agent (D)>

[0993] The structures of the acid diffusion control agent (D) used are shown below.

[0994] [Chemical formula 72]

[0995]

[0996] The surfactants used are shown below.

[0997] [Chemical formula 73]

[0998]

[0999] E-2: Megaface R-41 (manufactured by DIC Corporation)

[1000] E-3: KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[1001] E-4: Megaface F176 (manufactured by DIC Corporation)

[1002] E-5: Megaface R08 (manufactured by DIC Corporation)

[1003] The additives used are shown below.

[1004] [Chemical formula 74]

[1005]

[1006] The solvents used are shown below.

[1007] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[1008] S-2: Propylene glycol monomethyl ether (PGME)

[1009] S-3: Ethyl lactate

[1010] S-4: Ethyl 3-ethoxypropionate

[1011] S-5: 2-Heptanone

[1012] S-6: Methyl 3-methoxypropionate

[1013] S-7: Butyl 3-methoxyacetate

[1014] S-8: Butyl acetate

[1015] (Examples 1 to 35 and Comparative Examples 1 to 3)

[1016] (Preparation of a photosensitive or radiation-sensitive resin composition) (KrF exposure)

[1017] (Examples 1 to 7, 10 to 16, 19 to 31, 35, Comparative Examples 1 to 3)

[1018] The respective components shown in Table 1 were mixed at the contents (mass %) recorded in Table 1 to obtain a solution having the solid component concentration (mass %) recorded in Table 1. Subsequently, the obtained solution was filtered using a polyethylene filter having a pore size of 3 μm, thereby preparing a photosensitized or radiation-sensitive resin composition (resist composition).

[1019] In addition, in the resist composition, the solid components represent all components other than the solvent. The obtained resist composition was used in the examples and comparative examples.

[1020] In addition, in Table 1, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid components. Also, the usage amount (parts by mass) of the solvent used was recorded in the table.

[1021] <Pattern forming method (1): KrF exposure, development with an alkaline aqueous solution>

[1022] Using a spin coater “ACT-8” manufactured by Tokyo Electron Ltd., the resist composition prepared above was coated on a Si substrate (manufactured by Advanced Materials Technology Co., Ltd. (hereinafter, also referred to as “substrate”)) that had been subjected to hexamethyldisilazane treatment without providing an anti-reflection layer, and heat drying (PB) was performed at 150° C. for 60 seconds, thereby forming a resist film having a film thickness of 5 μm.

[1023] For this resist film, through a mask having a line-and-space pattern with a space pattern of 250 nm and a pitch of 1000 nm after reduction projection exposure and positive-type development, using a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C, wavelength 248 nm), pattern exposure was performed under exposure conditions of NA = 0.68 and σ = 0.60. After irradiation, baking (PEB) was performed at 130° C. for 60 seconds, and after immersing in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsing with water was performed for 30 seconds and drying was performed, thereby forming a line-and-space pattern with a space size of 250 nm and a pitch of 1000 nm.

[1024] Through exposure via the above mask, the exposure amount at which the formed line-and-space pattern has a space size of 250 nm and a pitch of 1000 nm was set as the optimum exposure amount, and this optimum exposure amount was set as the sensitivity (mJ / cm 2 ). The measurement of the space pattern width was performed using a scanning electron microscope (SEM: Scanning Electron Microscope) (model 9380II manufactured by Hitachi High-Technologies Corporation).

[1025] Through the above steps, an evaluation pattern wafer having a substrate and a pattern formed on the surface of the substrate was obtained.

[1026] <Performance Evaluation>

[1027] [Stability over Time]

[1028] After storing the resist composition at 40 °C for 4 weeks, a line-and-space pattern was formed in the same manner as above. In the obtained pattern, the sensitivity was determined in the same manner as above, and the difference in sensitivity between the pattern formed using the resist composition before storage over time and the pattern formed using the resist composition after storage over time (4 weeks at 40 °C), that is, the degree of sensitivity variation, was evaluated according to the following criteria.

[1029] (Criteria)

[1030] A: The observed sensitivity variation is less than 1 mJ / cm 2

[1031] B: The observed sensitivity variation is 1 mJ / cm 2 or more and less than 2 mJ / cm 2

[1032] C: The observed sensitivity variation is 2 mJ / cm 2 or more and less than 3 mJ / cm 2

[1033] D: The observed sensitivity variation is 3 mJ / cm 2 or more and less than 4 mJ / cm 2

[1034] E: The observed sensitivity variation is 4 mJ / cm 2 or more

[1035] <Preparation of a Photosensitive Radiation-Sensitive or Radiation-Sensitive Resin Composition> (ArF Exposure)

[1036] (Examples 8 - 9, 17 - 18, 32)

[1037] Each component shown in Table 1 was mixed at the contents (mass %) described in Table 1 to obtain a solution having the solid content concentration (mass %) described in Table 1. Subsequently, the obtained solution was filtered using a polyethylene filter having a pore size of 0.1 μm, thereby preparing a photosensitive radiation-sensitive or radiation-sensitive resin composition (resist composition). In addition, in the resist composition, the solid content represents all components except the solvent. The obtained resist composition was used in the examples.

[1038] In Table 1, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid components. Also, the amount used (parts by mass) of the solvent used is described in Table 1.

[1039] <Pattern formation method (2): ArF exposure, alkaline aqueous solution development (positive)>

[1040] On a Si substrate (manufactured by Advanced Materials Technology) that had been treated with hexamethyldisilazane, an antireflection layer was not provided, and the prepared resist composition was spin-coated at a rotational speed to achieve the target film thickness, and baked at a temperature of 120 °C for 60 seconds to form a photosensitive or radiation-sensitive film (resist film) having a film thickness of 700 nm.

[1041] For the wafer on which the resist film was formed, an ArF excimer laser scanner (manufactured by ASML, PAS5500 / 1500, wavelength 193 nm, NA 0.50) was used to perform pattern exposure through an exposure mask. Then, after baking at a temperature of 115 °C for 60 seconds, development was performed for 30 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH aq), rinsed with pure water, and then spin-dried. As a result, a line-and-space pattern with a space size of 250 nm and a pitch of 1500 nm was obtained.

[1042] The exposure amount at which the formed line-and-space pattern had a space size of 250 nm and a pitch of 1500 nm was defined as the optimum exposure amount, and this optimum exposure amount was defined as the sensitivity (mJ / cm 2 ). The measurement of the space pattern width was performed using a scanning electron microscope (SEM: Scanning Electron Microscope) (model 9380II manufactured by Hitachi High-Technologies Corporation).

[1043] Through the above steps, an evaluation pattern wafer having a substrate and a pattern formed on the surface of the substrate was obtained.

[1044] <Pattern formation method (3): ArF exposure, organic solvent development (negative)>

[1045] An exposure mask obtained by inverting the light-transmitting portion and the light-shielding portion of the exposure mask used in the above pattern formation method (2) (positive development) was used, and butyl acetate (organic developer) was used instead of the 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH aq), and methyl isobutyl carbinol (MIBC) was used instead of pure water. Otherwise, the same operations as those in the above pattern formation method (2) were performed, and thus a line-and-space pattern with a space size of 250 nm and a pitch of 1500 nm was obtained.

[1046] Set the exposure amount of the formed line and space pattern with a spatial size of 250 nm and a pitch of 1500 nm as the optimal exposure amount, and set this optimal exposure amount as the sensitivity (mJ / cm 2 ). The width of the space pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (Model 9380II manufactured by Hitachi High-Technologies Corporation).

[1047] <Performance Evaluation>

[1048] [Stability over Time]

[1049] After storing the resist composition at 40 °C for 4 weeks, a line and space pattern was formed in the same manner as above. In the obtained pattern, the sensitivity was determined in the same manner as above, and the difference in sensitivity between the pattern formed using the resist composition before storage over time and the pattern formed using the resist composition after storage over time (4 weeks at 40 °C), that is, the degree of sensitivity variation, was evaluated according to the following criteria.

[1050] (Judgment Criteria)

[1051] A: The observed sensitivity variation is less than 1 mJ / cm 2

[1052] B: The observed sensitivity variation is 1 mJ / cm 2 or more and less than 2 mJ / cm 2

[1053] C: The observed sensitivity variation is 2 mJ / cm 2 or more and less than 3 mJ / cm 2

[1054] D: The observed sensitivity variation is 3 mJ / cm 2 or more and less than 4 mJ / cm 2

[1055] E: The observed sensitivity variation is 4 mJ / cm 2 or more

[1056] <Preparation of a Photosensitive or Radiation-Sensitive Resin Composition> (EUV Exposure)

[1057] (Example 34)

[1058] The respective components shown in Table 1 were mixed at the contents (mass %) recorded in Table 1 to obtain a solution having the solid component concentration (mass %) recorded in Table 1. Subsequently, the obtained solution was filtered in the order of first a polyethylene filter with a pore size of 50 nm, then a nylon filter with a pore size of 10 nm, and finally a polyethylene filter with a pore size of 5 nm, thereby preparing a photosensitive or radiation-sensitive resin composition (resist composition).

[1059] In addition, in the resist composition, the solid components represent all components other than the solvent. The obtained resist composition was used in the examples.

[1060] In Table 1, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid components. Also, the amount (parts by mass) of the solvent used was recorded in Table 1.

[1061] <Pattern formation method (4): EUV exposure, alkali development (positive)>

[1062] ALA12 (manufactured by Brewer Science) was coated on a silicon wafer and baked at 205 °C for 60 seconds to form an underlayer film with a film thickness of 30 nm. The resist composition shown in the table was coated thereon and baked (PB) at 120 °C for 60 seconds to form a positive resist film with a film thickness of 30 nm.

[1063] Using an EUV exposure apparatus (manufactured by Exitech Corporation, Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), the resist film was irradiated with a pattern. In addition, as a reticle, a mask with a line size = 40 nm and a line:space = 1:1 was used.

[1064] After baking (PEB) the exposed resist film at 120 °C for 60 seconds, it was developed with an aqueous solution of tetramethylammonium hydroxide (TMAH, 2.38 mass %) for 30 seconds, and then rinsed with pure water for 30 seconds. By rotating the silicon wafer at a speed of 4000 rpm for 30 seconds and then baking it at 90 °C for 60 seconds, a line-and-space pattern with a pitch of 80 nm and a line width of 40 nm (space width of 40 nm) was obtained.

[1065] In addition, the optimum exposure dose (sensitivity) (mJ / cm 2). In the determination of the above sensitivity, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (Model 9380II manufactured by Hitachi High-Technologies Corporation).

[1066] Through the above steps, an evaluation pattern wafer having a substrate and a pattern formed on the surface of the substrate was obtained.

[1067] <Performance Evaluation>

[1068] [Stability over Time]

[1069] After storing the resist composition at 40 °C for 4 weeks, a line and space pattern was formed in the same manner as above. In the obtained pattern, the sensitivity was determined in the same manner as above, and the difference in sensitivity between the pattern formed using the resist composition before storage over time and the pattern formed using the resist composition after storage over time (4 weeks at 40 °C), that is, the degree of sensitivity variation, was evaluated according to the following criteria.

[1070] (Criteria)

[1071] A: The observed sensitivity variation is less than 1 mJ / cm 2

[1072] B: The observed sensitivity variation is 1 mJ / cm 2 or more and less than 2 mJ / cm 2

[1073] C: The observed sensitivity variation is 2 mJ / cm 2 or more and less than 3 mJ / cm 2

[1074] D: The observed sensitivity variation is 3 mJ / cm 2 or more and less than 4 mJ / cm 2

[1075] E: The observed sensitivity variation is 4 mJ / cm 2 or more

[1076] <Preparation of a Photosensitive or Radiation-Sensitive Resin Composition> (EB Exposure)

[1077] (Example 33)

[1078] The various components shown in Table 1 were mixed and a solution was obtained by mixing them to achieve the solid component concentrations (mass %) described in Table 1. The obtained liquid was filtered using a polytetrafluoroethylene filter having a pore size of 0.03 μm, thereby obtaining a photosensitive radiation-sensitive or radiation-sensitive resin composition (resist composition).

[1079] In addition, in the resist composition, the solid components represent all components other than the solvent. The obtained resist composition was used in the examples.

[1080] In Table 1, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid components. Also, the amount (parts by mass) of the solvent used was described in Table 1.

[1081] <Pattern Formation Method (5): EB Exposure, Alkaline Development (Positive)>

[1082] The resist composition shown in Table 1 was spin-coated on a 6-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron Ltd., and baked (PB) on a hot plate at 110 °C for 90 seconds, thereby obtaining a resist film with a film thickness of 80 nm.

[1083] The resist film was pattern-irradiated using an electron beam lithography apparatus (manufactured by ELIONIX INC.; ELS-7500, acceleration voltage 50 KeV). In addition, as a reticle, a mask with a line size = 100 nm and a line:space = 1:1 was used. After irradiation, it was baked (PEB) on a hot plate at 110 °C for 90 seconds, immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide as a developer for 60 seconds, and then rinsed with pure water for 30 seconds and dried, thereby obtaining a line-and-space pattern with a pitch of 200 nm, a line width of 100 nm (space width of 100 nm).

[1084] In addition, the optimum exposure dose (sensitivity) (μC / cm 2 ) for forming a line-and-space (LS) pattern with a pitch of 200 nm and a line width of 100 nm was set. In the determination of the above sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (model 9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern.

[1085] Through the above steps, an evaluation pattern wafer having a substrate and a pattern formed on the surface of the substrate was obtained.

[1086] <Performance Evaluation>

[1087] [Storage Stability over Time]

[1088] After storing the resist composition at 40 °C for 4 weeks, line and space patterns were formed in the same manner as described above. In the obtained patterns, the sensitivity was determined in the same manner as described above, and the difference in sensitivity between the pattern formed using the resist composition before storage over time and the pattern formed using the resist composition after storage over time (4 weeks at 40 °C), that is, the degree of sensitivity variation, was evaluated according to the following criteria.

[1089] (Criteria)

[1090] A: The observed sensitivity variation is less than 1 μC / cm 2

[1091] B: The observed sensitivity variation is 1 μC / cm 2 or more and less than 2 μC / cm 2

[1092] C: The observed sensitivity variation is 2 μC / cm 2 or more and less than 3 μC / cm 2

[1093] D: The observed sensitivity variation is 3 μC / cm 2 or more and less than 4 μC / cm 2

[1094] E: The observed sensitivity variation is 4 μC / cm 2 or more

[1095] The evaluation results obtained are shown in Table 2 below.

[1096]

[1097]

[1098] Table 2

[1099]

[1100] From the results in Table 2, it can be seen that the storage stability over time of the composition of the present invention is extremely excellent.

[1101] Industrial Applicability

[1102] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition capable of achieving extremely excellent storage stability over time.

[1103] According to the present invention, it is further possible to provide a photosensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the above photosensitive or radiation-sensitive resin composition.

[1104] The present invention has been described in detail with reference to specific embodiments, but it will be apparent to those skilled in the art that various changes or modifications can be added without departing from the spirit and scope of the present invention.

[1105] In addition, this application is based on a Japanese patent application filed on February 27, 2020 (Japanese Patent Application 2020-32446), the content of which is incorporated herein by reference.

Claims

1. A photosensitive actinic-ray or radiation-sensitive resin composition, comprising: (A) a resin; and (B) a compound represented by the following general formula (1) that generates an acid upon irradiation with actinic rays or radiation, In general formula (1), W1 represents a ring, Q represents a divalent linking group in which one or more ring members constituting the ring W1 are heteroatoms, carbonyl carbon atoms, or a combination thereof, R 1A and R 1B each independently represents a hydrogen atom, an organic group or a halogen atom, wherein, R 1A and R 1B at least one of which represents an organic group or a halogen atom, R 2A and R 2B each independently represents a hydrogen atom, an organic group or a halogen atom, wherein at least one of 2A R 2B and represents an organic group or a halogen atom p represents 0 or 1, q represents 0 or 1, wherein p + q represents 1 or 2, R1 and R2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group, provided that at least one of R1 and R2 represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group, n represents 1, R3 and R4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group, m represents an integer of 1 or more, L represents a carbonyl bond or an ester bond, l represents 1, At least two of R5 to R9 are optionally connected to each other to form a ring, R5, R6, R7, R8, and R9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or a cycloalkylthio group, Z - represents an anion.

2. The photosensitive actinic-ray or radiation-sensitive resin composition according to claim 1, wherein in the general formula (1), the ring W1 is a 6- to 8-membered ring.

3. The photosensitive actinic-ray or radiation-sensitive resin composition according to claim 1 or 2, wherein The R 1A and R 1B represent a cyano group as the organic group.

4. The photosensitive actinic-ray or radiation-sensitive resin composition according to claim 1 or 2, wherein The said R 2A and R 2B represent a cyano group as the organic group.

5. The photosensitive actinic-ray or radiation-sensitive resin composition according to claim 1 or 2, wherein In general formula (1), Z - is an anion represented by any one of the following general formulas (3) to (5), In general formula (3), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, L1 represents a single bond or a divalent linking group, A represents a monovalent organic group, x represents an integer of 1 to 20, In general formula (4), Xf1 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and two Xf1 are optionally connected to each other to form a ring structure, In general formula (5), Xf2 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and two Xf2 are optionally connected to each other to form a ring structure.

6. The photosensitive actinic-ray or radiation-sensitive resin composition according to claim 1 or 2, wherein in the general formula (1), Q is any linking group selected from the following group, In the above formula, R 11 represents a hydrogen atom or a substituent, * represents a bonding site to the group adjacent to Q that forms W1 in general formula (1).

7. The photosensitive actinic-ray or radiation-sensitive resin composition according to claim 1 or 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2), In general formula (2), Ra to Rd each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group, provided that at least one of Ra to Rd represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group, Q has the same meaning as Q in the above general formula (1), The meanings of R1 and R2 are the same as those of R1 and R2 in the above general formula (1). The meanings of R5, R6, R7, R8 and R9 are the same as those of R5, R6, R7, R8 and R9 in the above general formula (1). At least two of R5 to R9 are optionally connected to each other to form a ring. Z - has the same meaning as Z in the general formula (1) above - .

8. The photosensitive radiation-curable or radiation-sensitive resin composition according to claim 1 or 2, wherein In the general formula (1), at least one of R5 to R9 represents an alkoxy group, a cycloalkoxy group, an alkylthio group or a cycloalkylthio group.

9. The photosensitive radiation-curable or radiation-sensitive resin composition according to claim 7, wherein In the general formula (2), at least one of R5 to R9 represents an alkoxy group, a cycloalkoxy group, an alkylthio group or a cycloalkylthio group.

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

11. The photosensitive radiation-curable or radiation-sensitive resin composition according to claim 1 or 2, wherein The resin (A) has phenolic hydroxyl groups.

12. The photosensitive radiation-curable or radiation-sensitive resin composition according to claim 1 or 2, wherein The resin (A) has carboxyl groups.

13. A photosensitive radiation-curable or radiation-sensitive film formed by the photosensitive radiation-curable or radiation-sensitive resin composition according to any one of claims 1 to 12.

14. A pattern forming method, comprising: A step of exposing the photosensitive radiation-curable or radiation-sensitive film according to claim 13; And A step of developing the exposed photosensitive radiation-curable or radiation-sensitive film using a developer.

15. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 14.

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