Photosensitive or radiation-sensitive resin composition, photosensitive or radiation-sensitive film, pattern forming method, and method for manufacturing electronic devices.

Abstract

To provide an actinic ray-sensitive or radiation-sensitive resin composition that can reduce defects in a pattern after the lapse of time, while suppressing the occurrence of cracks in a pattern, and an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device that use the actinic ray-sensitive or radiation-sensitive resin composition.SOLUTION: There is provided an actinic ray-sensitive or radiation-sensitive resin composition having a concentration of solid contents of 15% or more, the resin composition containing (A) a resin including a repeating unit (a1) having an acid-decomposable group and a repeating unit (a2) having an aromatic ring, (B) a resin including a repeating unit (b1) represented by a specified general formula (1), and (C) a compound that generates an acid upon irradiation with an actinic ray or a radiation. A content of a repeating unit having an acid-decomposable group included in the resin (B) is 5 mol % or less relative to all repeating units in the resin (B).SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), microfabrication is performed using lithography with photosensitive or radiation-sensitive resin compositions. One lithography method involves forming a resist film using a photosensitive or radiation-sensitive resin composition, then exposing the resulting resist film to light, and subsequently developing it to form a resist pattern. As a photosensitive or radiation-sensitive resin composition, those containing a resin with repeating units having an acid-degradable group (acid-degradable resin) are known.

[0003] In recent years, photosensitive or radiation-sensitive resin compositions suitable for pattern formation using thick resist films have also been proposed (see, for example, Patent Document 1). Patent Document 1 describes a resist composition comprising a resin component containing repeating units having acid-degradable groups and a plasticizer component that does not contain acid-dissociable groups. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2021-92659 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, cracks tend to occur easily when forming patterns using thick resist films. Furthermore, our own research has shown that there is room for further improvement in reducing defects in patterns formed after the pattern-forming composition has been stored over time (hereinafter, these defects are also simply referred to as "defects in patterns after time has passed").

[0006] The object of the present invention is to provide a photosensitive or radiation-sensitive resin composition that can suppress the occurrence of cracks in the pattern while reducing defects in the pattern over time, as well as a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device using the above photosensitive or radiation-sensitive resin composition. [Means for solving the problem]

[0007] The inventors have found that the above problems can be solved by the following configuration.

[0008] [1] The solid content concentration is 15% or more. (A) A resin containing a repeating unit (a1) having an acid-degradable group and a repeating unit (a2) having an aromatic ring. (B) Resin containing a repeating unit (b1) represented by the following general formula (1) (C) Compounds that generate acid upon irradiation with active light or radiation. A photosensitive or radiation-sensitive resin composition containing, A photosensitive or radiation-sensitive resin composition wherein the content of repeating units having acid-degradable groups in the above resin (B) is 5 mol% or less relative to the total repeating units in resin (B).

[0009] [ka]

[0010] In general formula (1), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group. AL represents a linear or branched alkylene group. When n is an integer greater than or equal to 2, multiple AL groups may be identical or different. However, AL does not contain an acid-degradable group. Y represents -O-, -S-, -COO-, or -OCO-. When n represents an integer greater than or equal to 2, multiple Ys may be the same or different. The sum of the atomic weights of the atoms constituting the -(AL-Y-)n-R2 site is 70 or greater. n represents an integer greater than or equal to 1.

[0011] [2] The photosensitive or radiation-sensitive resin composition according to [1], wherein the resin (B) substantially contains no fluorine atoms and silicon atoms. [3] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the sum of the atomic weights of the atoms constituting the -(AL-Y-)n-R2 moiety is 80 or more.

[0012] [4] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein n in the above general formula (1) is an integer of 2 or more. [5] A photosensitive or radiation-sensitive resin composition according to any one of items [1] to [4], wherein the repeating unit (b1) is a repeating unit represented by the following general formula (2).

[0013] [ka]

[0014] In general formula (2), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group. AL represents a linear or branched alkylene group. When n is an integer greater than or equal to 2, multiple AL groups may be identical or different. However, AL does not contain an acid-degradable group. The sum of the atomic weights of the atoms constituting the -(AL-O-)n-R2 site is 70 or more. n represents an integer greater than or equal to 1.

[0015] [6] The photosensitive or radiation-sensitive resin composition according to any one of items [1] to [5], wherein the repeating unit (b1) is a repeating unit represented by the following general formula (3).

[0016] [ka]

[0017] In general formula (3), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group. The sum of the atomic weights of the atoms constituting the -(CH2CH2-O-)n-R2 site is 70 or more. n represents an integer greater than or equal to 1.

[0018] [7] The above resin (B) comprises a repeating unit (b2) having a carboxyl group or a hydroxyl group, as described in any one of [1] to [6]. [8] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the content of the above resin (B) is 40 parts by mass or less per 100 parts by mass of the above resin (A).

[0019] [9] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the molar content of the repeating unit (b1) contained in the resin (B) is 25 mol% or more relative to the total repeating units in the resin (B).

[10] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the amount of compound (C) contained in the above composition is 3 to 20 parts by mass per 100 parts by mass of resin (B).

[0020]

[11] A photosensitive or radiation-sensitive film formed from a photosensitive or radiation-sensitive resin composition described in any one of items [1] to

[10] .

[12] A pattern forming method comprising the steps of: forming an active photosensitive or radiation-sensitive film on a substrate using an active photosensitive or radiation-sensitive resin composition described in any one of items [1] to

[10] ; exposing the active photosensitive or radiation-sensitive film; and developing the exposed active photosensitive or radiation-sensitive film using a developer to form a pattern.

[13] A method for manufacturing an electronic device, including the pattern formation method described in

[12] . [Effects of the Invention]

[0021] According to the present invention, it is possible to provide a photosensitive or radiation-sensitive resin composition that can suppress the occurrence of cracks in the pattern while reducing defects in the pattern over time, as well as a photosensitive or radiation-sensitive film using the above photosensitive or radiation-sensitive resin composition, a pattern formation method, and a method for manufacturing an electronic device. [Modes for carrying out the invention]

[0022] An example of an embodiment for carrying out the present invention is described below.

[0023] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0024] In this specification, when a group (atomic group) is not specified as substituted or unsubstituted, it includes both substituted and unsubstituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" refers to a group containing at least one carbon atom.

[0025] Furthermore, in this specification, the type of substituent, the position of the substituent, and the number of substituents are not particularly limited when we say "may have substituents." The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic atom groups excluding hydrogen atoms, and for example, substituents T can be selected from the following.

[0026] (substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl; and methyl Alkylsulfanil groups such as sulfanil groups and tert-butylsulfanil groups; arylsulfanil groups such as phenylsulfanil groups and p-tolylsulfanil groups; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups; formyl groups; and combinations thereof.

[0027] In this specification, the bonding direction of divalent groups is not limited unless otherwise specified. For example, in a compound represented by the general formula "LMN", if M is -OCO-C(CN)=CH-, and the position where it is bonded on the L side is *1 and the position where it is bonded on the N side is *2, then M may be *1-OCO-C(CN)=CH-*2 or *1-CH=C(CN)-COO-*2.

[0028] In this specification, "(meth)acrylic" is a general term that includes acrylic and methacrylic, and means "at least one of acrylic and methacrylic." Similarly, "(meth)acrylic acid" is a general term that includes acrylic acid and methacrylic acid, and means "at least one of acrylic acid and methacrylic acid."

[0029] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), Z-average molecular weight (Mz), and molecular weight distribution (also referred to as dispersion) (Mw / Mn) of a resin are defined as polystyrene-converted values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (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 / min, detector: differential refractive index detector).

[0030] In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV), X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light, X-rays, and EUV, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.

[0031] [Actinic ray-sensitive or radiation-sensitive resin composition] The photosensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") is The solid content concentration is 15% or more. (A) A resin containing a repeating unit (a1) having an acid-degradable group and a repeating unit (a2) having an aromatic ring. (B) Resin containing a repeating unit (b1) represented by the following general formula (1) (C) Compounds that generate acid upon irradiation with active light or radiation. A photosensitive or radiation-sensitive resin composition containing, The above resin (B) contains an active photosensitive or radiation-sensitive resin composition in which the amount of repeating units having acid-degradable groups is 5 mol% or less relative to the total amount of repeating units in resin (B).

[0032] [ka]

[0033] In general formula (1), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group. AL represents a linear or branched alkylene group. When n is an integer greater than or equal to 2, multiple AL groups may be identical or different. However, AL does not contain an acid-degradable group. Y represents -O-, -S-, -COO-, or -OCO-. When n represents an integer greater than or equal to 2, multiple Ys may be the same or different. The sum of the atomic weights of the atoms constituting the -(AL-Y-)n-R2 site is 70 or greater. n represents an integer greater than or equal to 1.

[0034] The reason why the composition of the present invention can suppress the occurrence of cracks in the pattern while reducing defects in the pattern over time is not fully clear, but the inventors speculate as follows. Firstly, in pattern formation using thick photosensitive or radiation-sensitive films (hereinafter also simply referred to as "photosensitive films"), cracks are prone to occurring in the patterns. This is presumed to be because, in each step of the pattern formation method, such as the formation of the coating film, the drying of the coating film, and exposure of the photosensitive film obtained by drying, the stress caused by the volume change of the film resulting from the volatilization of solvent from the coating film and residual solvent from the photosensitive film is particularly large when using thick photosensitive films. One possible method to suppress the occurrence of cracks is to add a plasticizer to the composition that can soften the photosensitive film in order to relieve the stress mentioned above. However, our investigations have shown that while increasing the molecular weight of a plasticizer makes it easier to suppress crack formation, it also reduces its compatibility with the resin used in the composition, leading to a gradual tendency for the plasticizer to aggregate. Compositions for forming thick photosensitive films generally have a high solid content concentration, making them prone to aggregation of their components (e.g., plasticizers) during storage over time, and there was room for improvement regarding defects in the pattern after aging. Therefore, the inventors first focused on the structure of resin (B) contained in the composition of the present invention, which is expected to function as a plasticizer in the film. The repeating unit (b1) has a polar group as Y, and the sum of the atomic weights of the atoms constituting the -(AL-Y-)n-R2 portion is 70 or more, resulting in a structure with a large molecular weight in the side chain. This is thought to improve compatibility with resin (A) and make it easier to relieve stress in the resulting film. Thus, because resin (B) has the structure of the repeating unit (b1) described above, its compatibility with resin (A) is improved, and it is believed that even when the composition of the present invention is stored over time, the aggregation of resin (B) can be suppressed and it can be uniformly dispersed. As a result, it is believed that the above-mentioned stress in the film obtained by the composition can be relieved and the occurrence of cracks in the resulting pattern can be suppressed. Furthermore, it is believed that the mass distribution of resin (B) in the film obtained by the composition after storage over time can be made uniform, and consequently, the number of defects in the resulting pattern can be reduced. In particular, as mentioned above, compositions for forming thick films generally have a high solid content concentration, and it is thought that aggregation of plasticizers that may be contained in the composition is likely to occur during storage over time. However, the composition of the present invention, as specified above, has a high solid content concentration of 15% or more, and even with this high solid content concentration, it is possible to suppress the aggregation of resin (B) to an extremely high level, as described above. Therefore, it is presumed that the occurrence of cracks in the resulting pattern can be suppressed, and defects in the pattern after time can be reduced.

[0035] The photosensitive or radiation-sensitive resin composition of the present invention is typically a resist composition (preferably a chemically amplified resist composition), and may be either a positive-type resist composition or a negative-type resist composition. Furthermore, the photosensitive or radiation-sensitive resin composition of the present invention may be a resist composition for alkaline development or a resist composition for organic solvent development.

[0036] <Resin (A) containing a repeating unit (a1) having an acid-degradable group and a repeating unit (a2) having an aromatic ring> The present invention describes a resin (A) (also simply referred to as "resin (A)") which includes a repeating unit (a1) having an acid-degradable group and a repeating unit (a2) having an aromatic ring, as contained in the composition of the present invention.

[0037] (Repeating unit having an acid-degradable group (a1)) First, we will describe the repeating unit (a1) having an acid-degradable group (hereinafter also referred to as "repeating unit (a1)"). The resin (A) has repeating units (a1) that have acid-degradable groups. An acid-degradable group is a group that decomposes upon the action of an acid, producing a polar group. It is preferable that the acid-degradable group has a structure in which the polar group is protected by a leaving group (a group that is eliminated upon the action of an acid). In other words, it is preferable that resin (A) has repeating units having a group that decomposes upon the action of an acid, producing a polar group. It is preferable that resin (A) increases in polarity upon the action of an acid, increasing its solubility in alkaline developers and decreasing its solubility in organic solvents.

[0038] Preferred polar groups are alkali-soluble groups, such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. Preferred polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups.

[0039] Examples of groups that are eliminated by the action of an acid (leaving groups) include those represented by formulas (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0040] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may combine to form a monocycle or polycycle. The alkyl groups Rx1 to Rx3 are preferably C1 to C4 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, with monocyclic cycloalkyl groups having 5 to 6 carbon atoms being more preferred. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. The group represented by formula (Y1) or formula (Y2) is preferably such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the cycloalkyl group described above.

[0041] In formula (Y3), R 36 ~R 38 Each of these independently represents a hydrogen atom or a monovalent substituent. 37 and R 38 These may bond to each other to form a ring. The monovalent substituent is not particularly limited, but examples include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. 36 It is also preferable that it be a hydrogen atom.

[0042] For formula (Y3), a group represented by the following formula (Y3-1) is preferred.

[0043] [ka]

[0044] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group which may have a heteroatom, a cycloalkyl group which may have a heteroatom, an aryl group which may have a heteroatom, an amino group which may have an ammonium group which may have a mercapto group which may have a cyano group which may have an aldehyde group which may have a heteroatom, or a group which is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group). Alkyl and cycloalkyl groups may have, for example, one of their methylene groups replaced by a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. Preferably, one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. Q, M, and at least two of L1 may be bonded together to form a ring (preferably a 5-membered or 6-membered ring). In terms of pattern refinement, L2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, while examples of tertiary alkyl groups include tert-butyl and adamantane ring groups. In these embodiments, the glass transition temperature (Tg) and activation energy are increased, which ensures film strength and suppresses fogging.

[0045] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0046] As the repeating unit having an acid-degradable group, at least one of the repeating unit represented by the following general formula (Aa1) and the repeating unit represented by the following general formula (Aa2) is preferred.

[0047] [ka]

[0048] In the general formula (Aa1), L1 represents a divalent linking group, R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group, or an aryl group, and R2 represents a group that is eliminated by the action of an acid.

[0049] L1 represents a divalent linking group. Examples of divalent linking groups include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups formed by linking multiple such groups. The hydrocarbon groups may have substituents. L1 is preferably a -CO-, alkylene group, or -arylene group. As for the arylene group, an arylene group having 6 to 20 carbon atoms is preferred, an arylene group having 6 to 10 carbon atoms is more preferred, and a phenylene group is even more preferred. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The alkylene group preferably contains a fluorine atom or an iodine atom. The total number of fluorine atoms and iodine atoms contained in the alkylene group is not particularly limited, but 2 or more is preferred, 2 to 10 is more preferred, and 3 to 6 is even more preferred.

[0050] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group, or an aryl group. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. When the alkyl group has a fluorine atom or an iodine atom, the total number of fluorine atoms and iodine atoms contained in the alkyl group is not particularly limited, but 1 or more is preferable, 1 to 5 is more preferable, and 1 to 3 is even more preferable. The above alkyl group may have a heteroatom such as an oxygen atom other than a halogen atom.

[0051] R2 represents a group that is eliminated by the action of an acid (an elimination group). Examples of the elimination group include the groups represented by the above formulas (Y1) to (Y4), and the preferable ranges are the same as those described above.

[0052]

Chemical formula

[0053] In the general formula (Aa2), R 101 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group or an aryl group, and R 102 represents a group that is eliminated by the action of an acid.

[0054] R 101 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group or an aryl group. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable. When the alkyl group has a fluorine atom or an iodine atom, the total number of fluorine atoms and iodine atoms contained in the alkyl group is not particularly limited, but 1 or more is preferable, 1 to 5 is more preferable, and 1 to 3 is even more preferable. The above alkyl group may have a heteroatom such as an oxygen atom other than a halogen atom.

[0055] R 102 represents a group that is eliminated by the action of an acid (an elimination group). Examples of the elimination group include the groups represented by the above formulas (Y1) to (Y4), and the preferable ranges are the same as those described above.

[0056] Due to the large dissolution contrast before and after deprotection, the repeating unit having an acid-degradable group contained in resin (A) is preferably the repeating unit represented by the above general formula (Aa2), and more preferably the repeating unit represented by the following general formula (AI).

[0057] [ka]

[0058] In the general formula (AI), Xa1 represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Each of Rx1 to Rx3 independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, if all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Two of Rx1 to Rx3 may bond together to form a cycloalkyl group (monocyclic or polycyclic).

[0059] The alkyl group represented by Xa1 may have substituents. Examples of alkyl groups represented by Xa1 include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xa1 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent substituent. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0060] The divalent linking group represented by T may have substituents. Examples of divalent linking groups represented by T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0061] The alkyl groups Rx1 to Rx3 are preferably C1 to C4 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, and also preferably a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. The repeating unit represented by the general formula (AI) is preferably configured such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded together to form the cycloalkyl group described above.

[0062] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0063] The repeating unit represented by the general formula (AI) is preferably an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond).

[0064] The resin (A) may also preferably have at least one repeating unit selected from the group consisting of repeating units represented by the following general formulas (A-VIII) to (A-XII) as an acid-degradable repeating unit.

[0065] [ka]

[0066] In general formula (A-VIII), R5 represents a tert-butyl group, a 1,1'-dimethylpropyl group, or a -CO-O-(tert-butyl) group. In general formula (A-IX), R6 and R7 each independently represent a monovalent substituent. Examples of monovalent substituents include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. In the general formula (AX), p represents either 1 or 2. In the general formulas (AX) to (A-XII), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R9 represents an alkyl group having 1 to 3 carbon atoms. In general formula (A-XII), R 10 This represents an alkyl group or adamantyl group having 1 to 3 carbon atoms.

[0067] Resin (A) may have only one type of repeating unit having an acid-degradable group, or it may have two or more types.

[0068] The molar content of repeating units having acid-degradable groups in resin (A) (total content if there are two or more repeating units having acid-degradable groups) is preferably 70 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, particularly preferably 10 mol% to 40 mol%, and most preferably 15 mol% to 40 mol%. A content of repeating units having acid-degradable groups of 15 mol% or more is preferable because it allows for appropriate control of the dissolution contrast between the exposed and unexposed areas in the developer.

[0069] Resin (A) may have other repeating units in addition to the repeating units having acid-degradable groups.

[0070] (A repeating unit having an aromatic ring (a2)) Next, we will describe the repeating unit (a2) having an aromatic ring (hereinafter also referred to as "repeating unit (a2)"). The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heteroring.

[0071] The aromatic hydrocarbon ring may be monocyclic or polycyclic. For example, aromatic hydrocarbon rings with 6 to 20 carbon atoms can be used, specifically benzene rings, naphthalene rings, anthracene rings, and so on. Aromatic heterocycles may be monocyclic or polycyclic, and examples include thiophene rings, furan rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrrole rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, thiadiazole rings, and thiazole rings. The number of carbon atoms in the aromatic heterocycle is preferably 5 to 14, and more preferably 5 to 10.

[0072] In the repeating unit (a1) having an acid-degradable group, those having an aromatic ring are also included in the repeating unit (a2) having an aromatic ring.

[0073] The repeating unit (a2) is preferably the repeating unit represented by the following general formula (B).

[0074] [ka]

[0075] R3 represents a hydrogen atom or a monovalent substituent. The monovalent substituent may have a fluorine atom or an iodine atom. Examples of monovalent substituents include -L 40 A group represented by -R8 is preferred. 40 R8 represents a single bond or an ester group. R8 may be an alkyl group having a fluorine atom or an iodine atom, a cycloalkyl group having a fluorine atom or an iodine atom, an aryl group having a fluorine atom or an iodine atom, or a group combining these.

[0076] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

[0077] L2 represents a single bond or an ester group. L3 represents an (n+m+1) valent aromatic hydrocarbon ring group. Examples of aromatic hydrocarbon ring groups include benzene ring groups and naphthalene ring groups. R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). When R6 is a hydroxyl group, L3 is preferably an (n+m+1) valent aromatic hydrocarbon ring group. R7 represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. m represents an integer greater than or equal to 1. m is preferably an integer between 1 and 3, and more preferably an integer between 1 and 2. n represents an integer of 0 or greater than or equal to 1. Preferably, n is an integer between 1 and 4. (n+m+1) is preferably an integer between 1 and 5.

[0078] As a repeating unit (a2), a repeating unit represented by the following general formula (I) is also preferred.

[0079] [ka]

[0080] In general formula (I), R 41 , R 42 and R 43 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R 42 It may also be bonded to Ar4 to form a ring, in which case R 42 represents a single bond or an alkylene group. X4 is a single bond, -COO-, or -CONR 64 - represents R 64 represents a hydrogen atom or an alkyl group. L4 represents a single bond or an alkylene group. Ar4 represents an (n+1) valent aromatic ring group, R 42 When it combines with another element to form a ring, it represents an (n+2) valent aromatic ring group. n represents an integer between 1 and 5.

[0081] R in general formula (I) 41 , R 42 , and R 43 The alkyl group is preferably an alkyl group having 20 or fewer carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group; more preferably an alkyl group having 8 or fewer carbon atoms; and even more preferably an alkyl group having 3 or fewer carbon atoms.

[0082] R in general formula (I) 41 , R 42 , and R 43The cycloalkyl group can be monocyclic or polycyclic. Among these, monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl groups, are preferred. R in general formula (I) 41 , R 42 , and R 43 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine being preferred. R in general formula (I) 41 , R 42 , and R 43 The alkyl group included in the alkoxycarbonyl group is the above R 41 , R 42 , R 43 A alkyl group similar to the one in the example is preferred.

[0083] Ar4 represents an (n+1) valent aromatic ring group. When n is 1, the divalent aromatic ring group may have substituents, and preferred are aromatic ring groups containing heterocycles such as phenylene, torylene, naphthylene, and anthracenylene groups, or heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole rings.

[0084] Specific examples of (n+1)-valent aromatic ring groups when n is an integer greater than or equal to 2 include groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of divalent aromatic ring groups. The (n+1)-valent aromatic ring group may further have substituents.

[0085] The substituents that the alkyl groups, cycloalkyl groups, alkoxycarbonyl groups, alkylene groups, and (n+1)-valent aromatic ring groups mentioned above may have include, for example, R in general formula (I). 41 , R 42 , and R 43Examples include alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, and alkoxy groups such as butoxy groups; aryl groups such as phenyl groups; and so on. -CONR represented by X4 64 -(R 64 R in (where R represents a hydrogen atom or alkyl group) 64 Examples of alkyl groups include alkyl groups having 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups, with alkyl groups having 8 or fewer carbon atoms being preferred. X4 is preferably a single bond, -COO-, or -CONH-, and more preferably a single bond or -COO-.

[0086] In L4, the alkylene group is preferably a C1-C8 alkylene group such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, or octylene group. As for Ar4, an aromatic ring group having 6 to 18 carbon atoms is preferred, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are more preferred.

[0087] The following are specific examples of repeating units (a2), but the present invention is not limited thereto. In the formula, a represents 0, 1, 2, or 3. When a represents 1, 2, or 3, the following specific examples are examples of repeating units represented by general formula (I).

[0088] [ka]

[0089] [ka]

[0090] The resin (A) may have only one type of repeating unit (a2), or it may have two or more types.

[0091] The molar content of repeating units (a2) in resin (A) (total content if there are two or more types of repeating units (a2)) is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, particularly preferably 50 mol% to 85 mol%, and most preferably 55 mol% to 80 mol%.

[0092] The molar content of repeating units (a1) in resin (A) (total content if there are two or more types of repeating units (a1)) and the molar content of repeating units (a2) in resin (A) (total content if there are two or more types of repeating units (a2)) are preferably 80 mol% or more, and more preferably 85 mol% or more, relative to the total repeating units in resin (A). In one preferred embodiment, the resin (A) contains only repeating units (a1) and (a2).

[0093] The resin (A) may have other repeating units in addition to repeating units (a1) and (a2). The following describes other repeating units.

[0094] (A-2) A repeating unit having at least one selected from the group consisting of lactone structure, sultone structure, carbonate structure, and hydroxyadamantane structure. The resin (A) may have repeating units (A-2) having at least one selected from the group consisting of lactone structures, carbonate structures, sultone structures, and hydroxyadamantane structures.

[0095] The lactone structure or sultone structure in the repeating unit having a lactone structure or sultone structure is not particularly limited, but a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure is preferred, and a 5-7 membered ring lactone structure is more preferably one in which other ring structures are fused to form a bicyclo or spiro structure, or a 5-7 membered ring sultone structure is more preferably one in which other ring structures are fused to form a bicyclo or spiro structure. Examples of repeating units having a lactone or sultone structure include the repeating units described in paragraphs 0094 to 0107 of WO2016 / 136354.

[0096] The resin (A) may have repeating units having a carbonate structure. The carbonate structure is preferably a cyclic carbonate ester structure. Examples of repeating units having a carbonate structure include the repeating units described in paragraphs 0106-0108 of WO2019 / 054311.

[0097] The resin (A) may have repeating units having a hydroxyadamantane structure. Examples of repeating units having a hydroxyadamantane structure include the repeating unit represented by the following general formula (AIIa).

[0098] [ka]

[0099] In general formula (AIIa), R1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R2c to R4c each independently represent a hydrogen atom or a hydroxyl group. However, at least one of R2c to R4c represents a hydroxyl group. Preferably, one or two of R2c to R4c are hydroxyl groups and the rest are hydrogen atoms.

[0100] (Repeating units containing fluorine or iodine atoms) The resin (A) may have repeating units having fluorine atoms or iodine atoms. Examples of repeating units having fluorine atoms or iodine atoms include the repeating units described in paragraphs 0076 to 0081 of Japanese Patent Publication No. 2019-045864.

[0101] (Repeating unit with photoacid-generating group) Resin (A) may also have repeating units other than those described above, which include photoacid-generating groups (groups that generate acid upon irradiation with active light or radiation). Examples of repeating units having a photoacid generating group include the repeating units described in paragraphs 0092 to 0096 of Japanese Patent Publication No. 2019-045864.

[0102] (Repeating units having alkali-soluble groups) The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bisulfonylimide groups, and aliphatic alcohols substituted at the α-position with an electron-withdrawing group (e.g., hexafluoroisopropanol group), with carboxyl groups being preferred. The presence of repeating units with alkali-soluble groups in resin (A) increases resolution in contact hole applications. Examples of repeating units having alkali-soluble groups include repeating units in which alkali-soluble groups are directly bonded to the main chain of the resin, such as repeating units made of acrylic acid and methacrylic acid, or repeating units in which alkali-soluble groups are bonded to the main chain of the resin via a linking group. The linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. As repeating units having alkali-soluble groups, repeating units made of acrylic acid or methacrylic acid are preferred.

[0103] (Repeating units that do not possess either an acid-degradable group or a polar group) The resin (A) may further have repeating units that do not have either an acid-degradable group or a polar group. The repeating units that do not have either an acid-degradable group or a polar group preferably have an alicyclic hydrocarbon structure.

[0104] Examples of repeating units that do not have either an acid-degradable group or a polar group include the repeating units described in paragraphs 0236-0237 of U.S. Patent Application Publication No. 2016 / 0026083 and the repeating units described in paragraph 0433 of U.S. Patent Application Publication No. 2016 / 0070167.

[0105] In addition to the repeating structural units described above, resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc.

[0106] Resin (A) can be synthesized according to conventional methods (e.g., radical polymerization).

[0107] Weight-average molecular weight (Mw) of resin (A) A ) is preferably 1000 to 200000, more preferably 3000 to 50000, and even more preferably 5000 to 30000. A This is the polystyrene equivalent value measured by the GPC method described above.

[0108] Mw A The number average molecular weight of resin (A) Mn A The molecular weight distribution (Mw) of resin (A) is the value obtained by dividing by A / Mn A The molecular weight is typically 1.00 to 5.00, preferably 1.00 to 3.00, and more preferably 1.10 to 2.00. The smaller the molecular weight distribution, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the pattern and the better the roughness.

[0109] The mass-based content (S) of resin (A) relative to the total solid content in the composition of the present invention A The amount is preferably 40-95% by mass, and more preferably 60-95% by mass.

[0110] Resin (A) may be used alone or in combination of two or more types. When using two or more types of resin (A), it is preferable that their total amount is within the above range.

[0111] In this specification, "solids" refers to components other than the solvent. Even if the properties of the above components are liquid, they will be treated as solids. "Total solids" refers to the sum of all solids.

[0112] <Resin (B) containing a repeating unit (b1) represented by general formula (1)> The composition of the present invention contains a resin (B) (hereinafter also referred to as resin (B)) which includes a repeating unit (b1) represented by general formula (1).

[0113] [ka]

[0114] In general formula (1), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group. AL represents a linear or branched alkylene group. When n is an integer greater than or equal to 2, multiple AL groups may be identical or different. However, AL does not contain an acid-degradable group. Y represents -O-, -S-, -COO-, or -OCO-. When n represents an integer greater than or equal to 2, multiple Ys may be the same or different. The sum of the atomic weights of the atoms constituting the -(AL-Y-)n-R2 site is 70 or greater. n represents an integer greater than or equal to 1.

[0115] The hydrocarbon groups R1 and R2 are not particularly limited, but include alkyl groups, cycloalkyl groups, and aromatic ring groups. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but 3 to 15 is preferred, and 3 to 10 is more preferred.

[0116] The aromatic ring in the aromatic ring group may be an aromatic hydrocarbon ring or an aromatic heteroring.

[0117] The aromatic hydrocarbon ring may be monocyclic or polycyclic. For example, aromatic hydrocarbon rings with 6 to 20 carbon atoms can be used, specifically benzene rings, naphthalene rings, anthracene rings, and so on. Aromatic heterocycles may be monocyclic or polycyclic, and examples include thiophene rings, furan rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrrole rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, thiadiazole rings, and thiazole rings. The number of carbon atoms in the aromatic heterocycle is preferably 5 to 14, and more preferably 5 to 10.

[0118] Alkyl groups, cycloalkyl groups, and aromatic ring groups may have substituents. R 1 It is preferable that this represents a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. R 2 It is preferable that this represents a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0119] AL represents a linear or branched alkylene group. The linear or branched alkylene group is not particularly limited, but examples include linear or branched alkylene groups having 1 to 10 carbon atoms. The number of carbon atoms in the linear or branched alkylene group is preferably 1 to 5, and more preferably 1 to 2. Linear or branched alkylene groups may have substituents. AL does not have acid-degradable groups. The acid-degradable groups are the same as those in the repeating unit (a1) of resin (A) described above.

[0120] Y represents -O-, -S-, -COO-, or -OCO-. Y is preferably -O-, -S-, or -COO-, and more preferably -O- or -S-.

[0121] The sum of the atomic weights of the atoms constituting the -(AL-Y-)n-R2 moiety (hereinafter also simply referred to as "sum of atomic weights" or "side chain Mw") is 70 or greater. The sum of atomic weights is preferably 80 or more, and more preferably 90 or more. A sum of atomic weights of 80 or more is preferable because it increases the weight contribution of the side chains in resin (B), which increases the plasticizing effect of the resist film (improvement of stress relaxation), and makes it easier to reduce the occurrence of cracks in the resulting pattern. The sum of atomic weights is not particularly limited, but is preferably 300 or less, more preferably 250 or less, and even more preferably 200 or less. A sum of atomic weights of 200 or less is preferable because it allows for a more appropriate improvement in the plasticizing effect of the resist film and improved compatibility with resin (A).

[0122] n represents an integer of 1 or greater. Preferably, n represents an integer of 2 or greater. A higher molecular weight of the side chain is preferable because it increases the plasticizing effect on the resist film and makes it easier to reduce the occurrence of cracks in the resulting pattern. There is no particular upper limit to n, but it is usually 5 or less. n preferably represents an integer between 1 and 3, and more preferably represents 1 or 2.

[0123] The repeating unit (b1) is preferably a repeating unit represented by the following general formula (2). This can further improve the effect of plasticizing the resist film.

[0124] [ka]

[0125] In general formula (2), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group. AL represents a linear or branched alkylene group. When n is an integer greater than or equal to 2, multiple AL groups may be identical or different. However, AL does not contain an acid-degradable group. The sum of the atomic weights of the atoms constituting the -(AL-O-)n-R2 site is 70 or more. n represents an integer greater than or equal to 1.

[0126] R1, R2, AL, and n are the same as R1, R2, AL, and n in the above general formula (1), and the preferred ranges are also the same. The sum of the atomic weights of the atoms constituting the -(AL-O-)n-R2 site is 70 or more. The sum of the atomic weights of the atoms constituting the -(AL-O-)n-R2 site is the same as the sum of the atomic weights mentioned above, and the preferred range is also the same.

[0127] The repeating unit (b1) is preferably a repeating unit represented by the following general formula (3). The appropriate polarity of the ethylene oxy chain can further improve compatibility with resin (A) and reduce defects in the pattern over time.

[0128] [ka]

[0129] In general formula (3), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group. The sum of the atomic weights of the atoms constituting the -(CH2CH2-O-)n-R2 site is 70 or more. n represents an integer greater than or equal to 1.

[0130] R1, R2, and n are the same as R1, R2, and n in the general formula (1) above, and the preferred ranges are also the same. The sum of the atomic weights of the atoms constituting the -(CH2CH2-O-)n-R2 site is 70 or more. The sum of the atomic weights of the atoms constituting the -(CH2CH2-O-)n-R2 moiety is the same as the sum of the atomic weights mentioned above, and the preferred range is also the same.

[0131] The following are specific examples of the repeating unit (b1), but the present invention is not limited thereto. The sum of the atomic weights of the atoms constituting the -(AL-Y-)n-R2 site is also shown.

[0132] [ka]

[0133] The molar content of repeating units (b1) in resin (B) (total content if there are two or more types of repeating units (a2)) is preferably 100 mol% or less, more preferably 95 mol% or less, and even more preferably 90 mol% or less, relative to the total repeating units in resin (B). The molar content of repeating units (b1) in resin (B) (total content if there are two or more types of repeating units (a2)) is preferably 20 mol% or more, more preferably 25 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, relative to the total repeating units in resin (B).

[0134] (Repeating unit having a carboxyl group or a hydroxyl group (b2)) Resin (B) preferably contains repeating units (b2) having carboxyl groups or hydroxyl groups (also simply referred to as "repeating units (b2)"). It is preferable that resin (B) has repeating units having carboxylic acid groups or hydroxyl groups because it allows for appropriate adjustment of its compatibility with resin (A). When the repeating unit (b1) has a carboxyl group or a hydroxyl group, the repeating unit (b1) shall be included in the repeating unit (b2).

[0135] The repeating unit (b2) is preferably a repeating unit represented by the following general formula (2X).

[0136] [Chemical formula]

[0137] In the general formula (2X), R3 represents a hydrogen atom or an alkyl group. X represents a single bond or a linear or branched alkylene group -AL1-. AL1 represents -COO- or -O-. R4 represents a hydrogen atom.

[0138] The alkyl group of R3 may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but 1 to 3 is preferable, and 1 to 2 is more preferable. The linear or branched alkylene group of X is not particularly limited, but examples thereof include linear or branched alkylene groups having 1 to 10 carbon atoms. The number of carbon atoms of the linear or branched alkylene group is preferably 1 to 5, and more preferably 1 to 2. The linear or branched alkylene group may have a substituent. X preferably does not have an acid-decomposable group. The acid-decomposable group is the same as the acid-decomposable group in the repeating unit (a1) of the resin (A) described above.

[0139] The molar-based content of the repeating unit (b2) in the resin (B) (the total content when there are two or more repeating units (a2)) is preferably 100 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less with respect to all the repeating units in the resin (B). The molar content of repeating units (b2) in resin (B) (total content if there are two or more types of repeating units (a2)) is preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total repeating units in resin (B).

[0140] The resin (B) may have other repeating units in addition to the repeating unit (b1), (and, if it has a repeating unit (b2), the repeating unit (b2)). The following describes other repeating units. The resin (B) preferably has repeating units represented by the following general formula (3X) (hereinafter also referred to as repeating unit (3)).

[0141] [ka]

[0142] In general formula (3X), R5 represents a hydrogen atom or an alkyl group. R6 represents an alkyl group or cycloalkyl group.

[0143] The alkyl group of R5 may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 3 is preferred, and 1 to 2 is more preferred. R5 preferably represents a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0144] The alkyl group of R6 may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 20 is preferred, and 1 to 10 is more preferred. The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but 3 to 15 is preferred, and 3 to 10 is more preferred. The alkyl group and cycloalkyl group may have substituents. The substituents are not particularly limited, and examples thereof include a halogen atom, an alkoxy group (preferably having 1 to 10 carbon atoms), and the like.

[0145] The general formula (3X) may or may not have an acid-decomposable group, and it is preferably free of an acid-decomposable group.

[0146] Hereinafter, specific examples of the repeating unit (3) are shown, but the present invention is not limited thereto.

[0147]

Chemical formula

[0148] The molar-based content of the repeating unit (3) represented in the resin (B) (total content when having two or more repeating units (3)) is preferably 70 mol% or less, more preferably 60 mol% or less, and still more preferably 50 mol% or less with respect to all the repeating units in the resin (B). The molar-based content of the repeating unit (3) in the resin (B) (total content when having two or more repeating units (3)) is preferably 3 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more with respect to all the repeating units in the resin (B).

[0149] The content of the repeating unit having an acid-decomposable group contained in the resin (B) is 5 mol% or less with respect to all the repeating units in the resin (B). Examples of the repeating unit having an acid-decomposable group include the same ones as the repeating unit having an acid-decomposable group in the resin (A) above. The content of the amount of the repeating unit having an acid-decomposable group contained in the resin (B) is preferably 4 mol% or less, more preferably 3 mol% or less with respect to all the repeating units in the resin (B).

[0150] Resin (B) can be synthesized according to conventional methods (e.g., radical polymerization).

[0151] Weight-average molecular weight (Mw) of resin (B) B ) is preferably 5000 to 100000, more preferably 10000 to 90000, and even more preferably 12000 to 85000. Mw B By setting the above range, it becomes possible to appropriately adjust the solubility of resin (B) by obtaining an appropriate molecular weight, which is preferable. B This is the polystyrene equivalent value measured by the GPC method described above. Mw B The number average molecular weight of resin (B) Mn B The molecular weight distribution (Mw) of resin (B) is the value obtained by dividing by B / Mn B The ratio is usually between 1.00 and 5.00, preferably between 1.00 and 3.00, and more preferably between 1.10 and 2.00.

[0152] It is preferable that resin (B) is substantially free of fluorine and silicon atoms. This prevents resin (B) from becoming more hydrophobic and prevents them from being concentrated on the surface of the resulting film. Resin (B) preferably contains substantially no fluorine atoms or silicon atoms. Specifically, the content of repeating units having fluorine atoms or silicon atoms is preferably 5 mol% or less, more preferably 3 mol% or less, even more preferably 1 mol% or less, and ideally 0 mol%, i.e., it contains neither fluorine atoms nor silicon atoms.

[0153] The mass-based content of resin (B) relative to the total solid content in the composition of the present invention (S B The amount of ) is preferably 5 to 45% by mass, more preferably 5 to 35% by mass, and even more preferably 5 to 30% by mass.

[0154] Resin (B) may be used alone or in combination of two or more types. When using two or more types of resin (B), it is preferable that their total amount is within the above range.

[0155] The content of resin (B) in the composition of the present invention is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less, per 100 parts by mass of resin (A). This is preferable because the resulting film can be more appropriately adjusted by adjusting the content of resin (B) in the composition. The content of resin (B) in the composition of the present invention is more preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and even more preferably 10 to 20 parts by mass, per 100 parts by mass of resin (A).

[0156] <Compounds that generate acid upon irradiation with active light or radiation (C) (Photoacid Generators)> The composition of the present invention preferably contains a compound that generates acid upon irradiation with active light or radiation (also referred to as "photoacid generator (C)"). The photoacid generator (C) is not particularly limited as long as it is a compound that generates acid when irradiated with active light or radiation. The photoacid generator (C) may be in the form of a low molecular weight compound, or it may be incorporated as part of a polymer. Alternatively, both the low molecular weight compound form and the polymer-integrated form may be used in combination. When the photoacid generator (C) is in the form of a low molecular weight compound, its weight-average molecular weight (Mw) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. The photoacid generator (C) may be incorporated into a part of resin (A) or resin (B), or it may be incorporated into a resin different from resin (A) or resin (B). The photoacid generator (C) is preferably in the form of a low molecular weight compound. The photoacid generator (C) is preferably an ionic compound containing a cation and anion.

[0157] The photoacid generator (C) is preferably a compound that generates an organic acid upon irradiation with active light or radiation, and more preferably a compound that generates an organic acid upon irradiation with active light or radiation and has a fluorine atom or an iodine atom in its molecule. Examples of the above organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acid, bis(alkylsulfonyl)imide acid, and tris(alkylsulfonyl)methidic acid.

[0158] Preferred embodiments of the photoacid generator (C) include, for example, a compound represented by the following general formula (ZI), a compound represented by the following general formula (ZII), and a compound represented by the following general formula (ZIII).

[0159] [ka]

[0160] In the above general formula (ZI), R 201 , R 202 and R 203 Each of these independently represents an organic group. R 201 , R 202 and R 203 The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. Also, R 201 ~R 203 Two of these may bond together to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. 201 ~R 203 Examples of groups formed by the bonding of two of these groups include alkylene groups (e.g., butylene groups, pentylene groups) and -CH2-CH2-O-CH2-CH2-. Z - This represents an anion.

[0161] (Cations in compounds represented by the general formula (ZI)) Preferred embodiments of the cation in general formula (ZI) include the corresponding groups in compounds (ZI-1), (ZI-2), (ZI-3), and (ZI-4) described later. The photoacid generator (C) may be a compound having multiple structures represented by general formula (ZI). For example, R of a compound represented by general formula (ZI) 201 ~R 203 At least one of the above, and R of another compound represented by the general formula (ZI) 201 ~R 203 The compound may have a structure in which at least one of the compounds is bonded via a single bond or a linking group.

[0162] (Compound (ZI-1)) First, let me explain compound (ZI-1). Compound (ZI-1) is R of the above general formula (ZI) 201 ~R 203 An arylsulfonium compound is a compound in which at least one of the groups is an aryl group, i.e., a compound with an arylsulfonium cation. Aryl sulfonium compounds are R 201 ~R 203 All of them may be aryl groups, or R 201 ~R 203 A portion of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. Examples of arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0163] As the aryl group of the arylsulfonium compound, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium compound may have as necessary is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group can be mentioned.

[0164] R 201 ~R 203 The aryl group, alkyl group, and cycloalkyl group of ~R may each independently have an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to XIV carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

[0165] (Compound (ZI-2)) Next, the compound (ZI-2) will be described. The compound (ZI-2) is a compound in which R in the general formula (ZI) 201 ~R 203 each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom. R 201 ~R 203 The organic group having no aromatic ring as ~R generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. R 201 ~R 203is, independently of each other, preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and even more preferably a linear or branched 2-oxoalkyl group.

[0166] R 201 ~R 203 Examples of the alkyl group and cycloalkyl group of R~R include preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, and pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group). R 201 ~R 203 may be further substituted by a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0167] (Compound (ZI-3)) Next, the compound (ZI-3) will be described. Compound (ZI-3) is a compound represented by the following general formula (ZI-3) and having a phenacylsulfonium salt structure.

[0168] [Chemical formula]

[0169] In general formula (ZI-3), R 1c ~R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. R 6c and R 7cEach of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y Each of these independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y These may be bonded together to form a ring structure, and each of these ring structures may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Zc - This represents an anion.

[0170] R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y These may each bond to form a ring structure, and each of these ring structures may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the above-mentioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by the combination of two or more of these rings. Examples of ring structures include 3- to 10-membered rings, with 4- to 8-membered rings being preferred, and 5- or 6-membered rings being more preferred.

[0171] R 1c ~R 5c Two or more of the following, R 6c and R 7c , and R x and Ry Examples of groups formed by the bonding of these elements include butylene groups and pentylene groups. R 5c and R 6c , and R 5c and R x The group formed by the bonding is preferably a single bond or an alkylene group. Examples of alkylene groups include methylene groups and ethylene groups.

[0172] R 6c and R 7c The alkyl group is not particularly limited, but may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably having 1 to 15 carbon atoms, and even more preferably having 1 to 10 carbon atoms. Alkyl groups may have substituents.

[0173] R 6c and R 7c The cycloalkyl group is not particularly limited, but may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms. Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and decahydronaphthalenyl groups. The cycloalkyl group may have substituents.

[0174] R 6c and R 7c The aryl group is not particularly limited, but may be monocyclic or polycyclic, preferably having 6 to 20 carbon atoms, more preferably having 6 to 15 carbon atoms, and even more preferably having 6 to 10 carbon atoms. The aryl group may have substituents.

[0175] R 6c and R 7cEach of these is preferably independently a hydrogen atom, an alkyl group, or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group.

[0176] R X and R y The alkyl group is not particularly limited, but may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably having 1 to 15 carbon atoms, and even more preferably having 1 to 10 carbon atoms. Alkyl groups may have substituents.

[0177] R X and R y The cycloalkyl group is not particularly limited, but may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms. Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and decahydronaphthalenyl groups. The cycloalkyl group may have substituents.

[0178] R X and R y The 2-oxoalkyl group is not particularly limited, but is preferably a 2-oxoalkyl group having 1 to 20 carbon atoms, more preferably a 2-oxoalkyl group having 1 to 15 carbon atoms, and even more preferably a 2-oxoalkyl group having 1 to 10 carbon atoms. The 2-oxoalkyl group may have substituents.

[0179] R X and R y The 2-oxocycloalkyl group is not particularly limited, but is preferably a 2-oxocycloalkyl group having 3 to 20 carbon atoms, more preferably a 2-oxocycloalkyl group having 3 to 15 carbon atoms, and even more preferably a 2-oxocycloalkyl group having 3 to 10 carbon atoms. The 2-oxocycloalkyl group may have substituents.

[0180] R X and R y The alkoxycarbonylalkyl group is not particularly limited, but is preferably an alkoxycarbonylalkyl group having 3 to 22 carbon atoms, more preferably an alkoxycarbonylalkyl group having 3 to 17 carbon atoms, and even more preferably an alkoxycarbonylalkyl group having 3 to 12 carbon atoms. The alkoxycarbonylalkyl group may have substituents.

[0181] R X and R y These elements may be linked to each other to form a ring, and this ring structure may contain oxygen atoms, nitrogen atoms, sulfur atoms, ketone groups, ether bonds, ester bonds, and amide bonds. The above ring structure preferably contains an oxygen atom. Examples of the above-mentioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by the combination of two or more of these rings. Examples of ring structures include 3- to 10-membered rings, with 4- to 8-membered rings being preferred, and 5- or 6-membered rings being more preferred.

[0182] (Compound (ZI-4)) Next, we will explain compound (ZI-4). Compound (ZI-4) is represented by the following general formula (ZI-4).

[0183] [ka]

[0184] In the general formula (ZI-4), l represents an integer between 0 and 2. r represents an integer between 0 and 8. R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group. R 14 R represents a hydroxyl group, alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylsulfonyl group, or cycloalkylsulfonyl group. 14 If multiple instances exist, they may be identical or different. R 15 Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. 15 They may bond to each other to form a ring. Two R 15 When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. Z - This represents an anion.

[0185] In the general formula (ZI-4), R 13 , R 14 and R 15 The alkyl group is linear or branched, preferably having 1 to 10 carbon atoms, and more preferably a methyl group, ethyl group, n-butyl group, or t-butyl group.

[0186] R 13 The alkyl group is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group is preferred. Alkyl groups may have substituents.

[0187] R 13 The cycloalkyl group is not particularly limited, but may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms. Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and decahydronaphthalenyl groups. The cycloalkyl group may have substituents.

[0188] R 13 The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and even more preferably an alkoxy group having 1 to 10 carbon atoms. The alkoxy group may have substituents.

[0189] R 13 The alkoxycarbonyl group is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 21 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 16 carbon atoms, and even more preferably an alkoxycarbonyl group having 2 to 11 carbon atoms. The alkoxycarbonyl group may have substituents.

[0190] R 14 The alkyl group is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group is preferred. Alkyl groups may have substituents.

[0191] R 14 The cycloalkyl group is not particularly limited, but may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms. Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and decahydronaphthalenyl groups. The cycloalkyl group may have substituents.

[0192] R 14The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and even more preferably an alkoxy group having 1 to 10 carbon atoms. The alkoxy group may have substituents.

[0193] R 14 The alkoxycarbonyl group is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 21 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 16 carbon atoms, and even more preferably an alkoxycarbonyl group having 2 to 11 carbon atoms. The alkoxycarbonyl group may have substituents.

[0194] R 14 The alkylcarbonyl group is not particularly limited, but is preferably an alkylcarbonyl group having 2 to 21 carbon atoms, more preferably an alkylcarbonyl group having 2 to 16 carbon atoms, and even more preferably an alkylcarbonyl group having 2 to 11 carbon atoms. The alkoxycarbonyl group may have substituents.

[0195] R 14 The alkylsulfonyl group is not particularly limited, but is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, more preferably an alkylsulfonyl group having 1 to 15 carbon atoms, and even more preferably an alkylsulfonyl group having 1 to 10 carbon atoms. The alkylsulfonyl group may have substituents.

[0196] R 14 The cycloalkylsulfonyl group is not particularly limited, but is preferably a cycloalkylsulfonyl group having 3 to 20 carbon atoms, more preferably a cycloalkylsulfonyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkylsulfonyl group having 3 to 10 carbon atoms. The cycloalkylsulfonyl group may have substituents.

[0197] R 14 If there are multiple, then multiple R 14 They may be the same or different from one another.

[0198] R 15 The alkyl group is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group is preferred. Alkyl groups may have substituents.

[0199] R 15 The cycloalkyl group is not particularly limited, but may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms. Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and decahydronaphthalenyl groups. The cycloalkyl group may have substituents.

[0200] R 15 The naphthyl group may have substituents.

[0201] Two R's 15 They may bond to each other to form a ring. Two R 15 When these atoms bond to each other to form a ring, this ring structure may contain oxygen atoms, nitrogen atoms, sulfur atoms, ketone groups, ether bonds, ester bonds, and amide bonds. The above ring structure preferably contains an oxygen atom. Examples of the above-mentioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by the combination of two or more of these rings. Examples of ring structures include 3- to 10-membered rings, with 4- to 8-membered rings being preferred, and 5- or 6-membered rings being more preferred.

[0202] In one preferred embodiment, two R 15 It is preferable that the alkyl group is bonded to each other to form a ring structure.

[0203] (Cations in compounds represented by general formula (ZII) or general formula Z(III)) Next, we will explain the general formulas (ZII) and (ZIII). In general formulas (ZII) and (ZIII), R 204 ~R 207 Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 ~R 207 The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. 204 ~R 207 The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocyclic aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 ~R 207 Preferably, the alkyl and cycloalkyl groups are linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group).

[0204] R 204 ~R 207 The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. 204~R 207 Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. Z - This represents an anion.

[0205] (Anions in compounds represented by general formula (ZI), general formula (ZII), general formula (ZI-3), or general formula (ZI-4)) Z in general formula (ZI) - , Z in general formula (ZII) - , Zc in the general formula (ZI-3) - , and Z in general formula (ZI-4) - As such, an anion represented by the following general formula (3) is preferred.

[0206] [ka]

[0207] In general formula (3), Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. If there are multiple R4 and R5, they may be the same or different. L represents a divalent linking group, and if there are multiple Ls, they may be the same or different. W represents an organic group. o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0208] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Multiple Xf values ​​may be the same or different. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More preferably, Xf is a fluorine atom or CF3. In particular, it is preferable that all of Xf are fluorine atoms.

[0209] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. If multiple R4 and R5 are present, they may be the same or different. The alkyl groups R4 and R5 may have substituents, and preferably have 1 to 4 carbon atoms. R4 and R5 are preferably hydrogen atoms. Specific examples and preferred embodiments of alkyl groups substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in general formula (3).

[0210] L represents a divalent linking group, and if there are multiple Ls, they may be the same or different. Examples of divalent linking groups include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups that are combinations of several of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, or -NHCO-alkylene group- are preferred, and -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene group-, or -OCO-alkylene group- are more preferred.

[0211] W represents an organic group. The number of carbon atoms in the organic group is not particularly limited, but is generally 1 to 30, and preferably 1 to 20. The organic group is not particularly limited, but it can represent, for example, an alkyl group, an alkoxy group, etc. The alkyl group is not particularly limited, but may be linear or branched, and is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl and alkoxy groups may have substituents. The substituents are not particularly limited, but examples include the substituent T mentioned above, with fluorine atoms being preferred.

[0212] W preferably represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

[0213] The aryl group may be monocyclic or polycyclic. Examples of aryl groups include the phenyl group, naphthyl group, phenanthryl group, and anthryl group. The heterocyclic group may be monocyclic or polycyclic. Polycyclic groups are better able to suppress acid diffusion. The heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic groups include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocyclic groups include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. Examples of lactone and sultone rings include the lactone and sultone structures exemplified in the aforementioned resins. Among the heterocyclic groups, furan rings, thiophene rings, pyridine rings, or decahydroisoquinoline rings are particularly preferred.

[0214] The above cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acid ester groups. The carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbonyl carbons.

[0215] Z in general formula (ZI) - , Z in general formula (ZII) - , Zc in the general formula (ZI-3) - , and Z in general formula (ZI-4) - Anions represented by the following general formulas (An-2) or (An-3) are also preferred.

[0216] [ka]

[0217] In general formulas (An-2) and (An-3), Rfa independently represents a monovalent organic group having a fluorine atom, and multiple Rfa groups may bond to each other to form a ring.

[0218] Rfa is preferably an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0219] Preferred examples of sulfonium cations in general formula (ZI) and sulfonium cations or iodonium cations in general formula (ZII) are shown below.

[0220] [ka]

[0221] Anion Z in general formula (ZI) and general formula (ZII) - , Zc in the general formula (ZI-3) - , and Z in general formula (ZI-4) - A preferred example is shown below.

[0222] [ka]

[0223] The mass-based content of the photoacid generator (C) in the composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the composition.

[0224] The photoacid generator (C) may be used alone or in combination of two or more types. When using two or more photoacid generators (C) in combination, it is preferable that their total amount is within the above range.

[0225] The amount of compound (C) contained in the composition of the present invention is preferably 2 to 20 parts by mass per 100 parts by mass of resin (B). By adjusting the content of compound (C) in the composition, it is possible to generate sufficient acid necessary for deprotection while ensuring permeability in the thick resist film, which is preferable. The content of compound (C) in the composition of the present invention is more preferably 3 to 20 parts by mass, and even more preferably 4 to 18 parts by mass, per 100 parts by mass of resin (B).

[0226] <Acid diffusion control agent (D)> The composition of the present invention preferably contains an acid diffusion control agent (also referred to as "acid diffusion control agent (D)"). The acid diffusion control agent (D) traps the acid generated from the photoacid generator (C) etc. during exposure, and acts as a quencher to suppress the reaction of resin (A) and resin (B) (acid-degradable resin) in the unexposed areas due to excess generated acid. Examples of acid diffusion control agents (D) that can be used include basic compounds (DA), basic compounds whose basicity decreases or disappears upon irradiation with active light or radiation (DB), onium salts (DC) that are relatively weak acids with respect to the photoacid generator (C), low molecular weight compounds (DD) that have a nitrogen atom and a group that is eliminated by the action of an acid, and onium salt compounds (DE) that have a nitrogen atom in the cation portion. As the acid diffusion control agent (D), any known acid diffusion control agent can be used as appropriate. For example, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458 can be suitably used as the acid diffusion control agent (D).

[0227] Examples of basic compounds (DA) include those described in paragraphs 0188 to 0208 of Japanese Patent Publication No. 2019-045864.

[0228] In this invention, an onium salt (DC), which is a relatively weak acid with respect to the photoacid generator (C), can also be used as the acid diffusion control agent (D). When a photoacid generator (C) and an onium salt that generates an acid that is relatively weaker than the acid produced by the photoacid generator (C) are mixed and used, when the acid produced by the photoacid generator (C) collides with the onium salt containing an unreacted weak acid anion due to irradiation with active light or radiation, salt exchange occurs, releasing the weak acid and producing an onium salt containing a strong acid anion. In this process, the strong acid is exchanged for a weaker acid with lower catalytic activity, so it is thought that the acid is effectively deactivated and acid diffusion can be controlled.

[0229] Examples of onium salts that are relatively weak acids with respect to the photoacid generator (C) include the onium salts described in paragraphs 0224 to 0233 of Japanese Patent Publication No. 2019-070676.

[0230] Preferred basic compounds (DA) include compounds having the structures shown in the following formulas (A) to (E).

[0231] [ka]

[0232] In general formulas (A) and (E), R 200 , R 201 and R 202 These may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms), an alkylcarbonyl group (preferably having 2 to 21 carbon atoms), a cycloalkylcarbonyl group (preferably having 4 to 21 carbon atoms), an arylcarbonyl group (preferably having 7 to 21 carbon atoms), an alkylsulfonyl group (preferably having 1 to 20 carbon atoms), a cycloalkylsulfonyl group (preferably having 3 to 20 carbon atoms), or an arylsulfonyl group (preferably having 6 to 20 carbon atoms). 200 , R201 and R 202 At least two of these may be bonded together to form a ring, and this ring may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, a carbonyl group, and a sulfonyl group. R 203 , R 204 , R 205 and R 206 These may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0233] Regarding the alkyl group mentioned above, preferred alkyl groups having substituents are aminoalkyl groups having 1 to 20 carbon atoms, hydroxyalkyl groups having 1 to 20 carbon atoms, or cyanoalkyl groups having 1 to 20 carbon atoms. The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

[0234] Preferred basic compounds (DA) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, or piperidine, and more preferably compounds having an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure, or pyridine structure, alkylamine derivatives having a hydroxyl group and / or ether linkage, or aniline derivatives having a hydroxyl group and / or ether linkage.

[0235] Basic compounds (DB) (hereinafter also referred to as "compounds (DB)") whose basicity decreases or disappears upon irradiation with active light or radiation are compounds that have a proton-accepting functional group and decompose upon irradiation with active light or radiation, resulting in a decrease or disappearance of proton-accepting properties, or a change from proton-accepting properties to acidic properties.

[0236] A proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having electrons, and means, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom with a non-bonding electron pair that does not contribute to π-conjugation. The nitrogen atom having a non-bonding electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

[0237] [Chemical formula]

[0238] Preferred partial structures of the proton acceptor functional group include, for example, crown ether, azacrown ether, primary to tertiary amines, pyridine, imidazole, and pyrazine structures.

[0239] Compound (DB) decomposes upon irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property decreases or disappears, or changes from a proton acceptor property to acidity. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to acidity, is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, it means that the equilibrium constant in the chemical equilibrium decreases. The proton acceptor property can be confirmed by measuring the pH.

[0240] The acid dissociation constant pKa of the compound generated by the decomposition of compound (DB) upon irradiation with actinic rays or radiation preferably satisfies pKa < -1, more preferably -13 < pKa < -1, and even more preferably -13 < pKa < -3.

[0241] The acid dissociation constant pKa refers to the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in the Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). A lower value of the acid dissociation constant pKa indicates a higher acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by using an infinitely diluted aqueous solution and measuring the acid dissociation constant at 25°C. Alternatively, the value can be calculated using the software package 1 described below, based on a database of Hammett substituent constants and publicly available literature values. All pKa values ​​described herein are those calculated using this software package.

[0242] Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0243] In the composition of the present invention, an onium salt (DC), which is a relatively weak acid with respect to the acid generator, can be used as an acid diffusion control agent. When an acid generator and an onium salt that generates an acid that is relatively weaker than the acid produced by the acid generator are used in a mixture, the acid produced by the acid generator collides with the onium salt containing unreacted weak acid anions due to irradiation with active light or radiation. This results in salt exchange, releasing the weak acid and producing an onium salt containing strong acid anions. In this process, the strong acid is exchanged for a weaker acid with lower catalytic activity, so the acid appears to be deactivated, allowing for control of acid diffusion.

[0244] The onium salt that acts as a relatively weak acid with respect to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

[0245] [ka]

[0246] In the formula, R 51Z is a hydrocarbon group which may have substituents, 2c R is a hydrocarbon group having 1 to 30 carbon atoms, which may have substituents (provided that the carbon adjacent to S is not substituted with a fluorine atom), and 52 Y is an organic group, 3 Rf is a linear, branched, or cyclic alkylene group or arylene group, and Rf is a hydrocarbon group containing a fluorine atom, M + Each of these is independently an ammonium cation, a sulfonium cation, or an iodonium cation.

[0247] M + Preferred examples of sulfonium cations or iodonium cations represented as include the sulfonium cation exemplified by general formula (ZI) and the iodonium cation exemplified by general formula (ZII).

[0248] The onium salt (DC), which is a relatively weak acid with respect to the acid generator, may be a compound (hereinafter also referred to as "compound (DCA)") that has a cationic and anionic moiety within the same molecule, and in which the cationic and anionic moieties are covalently linked. The compound (DCA) is preferably a compound represented by any of the following general formulas (C-1) to (C-3).

[0249] [ka]

[0250] In general formulas (C-1) to (C-3), R1, R2, and R3 each independently represent a substituent having one or more carbon atoms. L1 represents a divalent linking group or single bond that connects the cation and anion moieties. -X - -COO - , -SO3 - , -SO2 - , and -N --R4 represents an anionic site selected from R4. R4 represents a monovalent substituent having at least one of the following at the linking site with the adjacent N atom: a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O)2-), and a sulfinyl group (-S(=O)-). R1, R2, R3, R4, and L1 may bond to each other to form a ring structure. In addition, in general formula (C-3), two of R1 to R3 may together represent a single divalent substituent, which may be bonded to the N atom by a double bond.

[0251] Examples of substituents having one or more carbon atoms in R1 to R3 include alkyl groups, cycloalkyl groups, aryl groups, alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, cycloalkylaminocarbonyl groups, and arylaminocarbonyl groups. Preferably, alkyl groups, cycloalkyl groups, or aryl groups are used.

[0252] Examples of L1 as a divalent linking group include linear or branched alkylene groups, cycloalkylene groups, arylene groups, carbonyl groups, ether bonds, ester bonds, amide bonds, urethane bonds, urea bonds, and groups formed by combining two or more of these. Preferably, L1 is an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

[0253] A low molecular weight compound (DD) (hereinafter also referred to as "compound (DD)") having a nitrogen atom and a group that is eliminated by the action of an acid is preferably an amine derivative having the group that is eliminated by the action of an acid on the nitrogen atom. The groups that are removed by the action of an acid are preferably acetal groups, carbonate groups, carbamate groups, tertiary ester groups, tertiary hydroxyl groups, or hemiaminal ether groups, with carbamate groups or hemiaminal ether groups being more preferred. The molecular weight of compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500. Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

[0254] [ka]

[0255] In general formula (d-1), Each Rb independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). Rb may be linked to each other to form a ring. The alkyl, cycloalkyl, aryl, and aralkyl groups represented by Rb may each be independently substituted with functional groups such as hydroxyl, cyano, amino, pyrrolidino, piperidino, morpholino, or oxo groups, alkoxy groups, or halogen atoms. The same applies to the alkoxyalkyl groups represented by Rb.

[0256] As Rb, linear or branched alkyl groups, cycloalkyl groups, or aryl groups are preferred, and linear or branched alkyl groups, or cycloalkyl groups are more preferred. Examples of rings formed by the interconnection of two Rb molecules include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and their derivatives. Specific structures of the base represented by general formula (d-1) include, but are not limited to, those disclosed in paragraph

[0466] of U.S. Patent Publication US2012 / 0135348A1.

[0257] The compound (DD) preferably has a structure represented by the following general formula (6).

[0258] [ka]

[0259] In general formula (6), l represents an integer between 0 and 2, and m represents an integer between 1 and 3, satisfying the condition l + m = 3. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may be linked together with the nitrogen atom in the formula to form a heterocycle. This heterocycle may contain heteroatoms other than the nitrogen atom in the formula. Rb is synonymous with Rb in the general formula (d-1) above, and the preferred example is also the same. In general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra may each be independently substituted with a group similar to those described above, which may be substituted with an alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb.

[0260] Specific examples of the alkyl, cycloalkyl, aryl, and aralkyl groups of Ra (these groups may be substituted with the above groups) are the same groups as those mentioned above for Rb. Specific structures of particularly preferred compounds (DD) in the present invention include, but are not limited to, those disclosed in paragraph

[0475] of U.S. Patent Application Publication 2012 / 0135348A1.

[0261] An onium salt compound (DE) having a nitrogen atom in the cation (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cation. The basic site is preferably an amino group, and more preferably an aliphatic amino group. It is even more preferable that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferable that electron-withdrawing functional groups (such as carbonyl groups, sulfonyl groups, cyano groups, and halogen atoms) are not directly bonded to the nitrogen atom. A preferred specific structure of compound (DE) is, but is not limited to, the compound disclosed in paragraph

[0203] of U.S. Patent Application Publication 2015 / 0309408A1.

[0262] The content of the acid diffusion control agent (D) in the composition of the present invention (the total if there are multiple types) is preferably 0.01 to 10.0% by mass, and more preferably 0.01 to 5.0% by mass, relative to the total solid content of the composition of the present invention. In the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more types.

[0263] <Solvent> The composition of the present invention preferably contains a solvent (also referred to as "solvent (S)"). The solvent (S) preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. In this case, the solvent may further contain components other than components (M1) and (M2). A solvent containing component (M1) or (M2) is preferable when used in combination with the aforementioned resins (A) and (B) because it improves the coatability of the photosensitive or radiation-sensitive resin composition and enables the formation of patterns with fewer development defects.

[0264] Examples of solvents (S) 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 compounds which may contain a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

[0265] The solvent (S) content in the composition of the present invention is preferably adjusted so that the solid content concentration of the composition of the present invention is 15 to 45% by mass, and more preferably so that the solid content concentration of the composition of the present invention is 20 to 45% by mass. The solid content concentration refers to the mass percentage of the mass of the other components (components that can constitute a photosensitive or radiation-sensitive film) excluding the solvent, relative to the total mass of the photosensitive or radiation-sensitive resin composition.

[0266] <Surfactants> The composition of the present invention may contain a surfactant (also referred to as "surfactant (E)"). By including a surfactant, the composition of the present invention can form patterns with superior adhesion and fewer development defects. As the surfactant (E), fluorine-based and / or silicone-based surfactants are preferred. Examples of fluorine-based and / or silicone-based surfactants include the surfactant described in paragraph 0276 of U.S. Patent Application Publication No. 2008 / 0248425. Also, F-Top EF301 or EF303 (manufactured by Shin Akita Chemical Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.), SC101, SC102, SC103, SC104, SC105 or SC106 (manufactured by Asahi Glass Co., Ltd.); Fluorocarbon S-393 (manufactured by Seimi Chemical Co., Ltd.); F-Top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Co., Ltd.); KH-20 (manufactured by Asahi Kasei Corporation); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Co., Ltd.) may also be used. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone-based surfactant.

[0267] Furthermore, in addition to the known surfactants described above, surfactant (E) may be synthesized using a fluoroaliphatic compound produced by telomerization (also known as telomerization) or oligomerization (also known as oligomerization). Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as the surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in Japanese Patent Publication No. 2002-90991. Preferably, the polymer having a fluoroaliphatic group is a copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene))acrylate and / or (poly(oxyalkylene))methacrylate, which may be irregularly distributed or block copolymerized. Examples of poly(oxyalkylene) groups include poly(oxyethylene) groups, poly(oxypropylene) groups, and poly(oxybutylene) groups, and may also be units having alkylenes of different chain lengths within the same chain length, such as poly(block linkage of oxyethylene, oxypropylene, and oxyethylene) or poly(block linkage of oxyethylene and oxypropylene). Furthermore, the copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene))acrylate (or methacrylate) may not only be a binary copolymer, but may also be a ternary or higher copolymer obtained by simultaneously copolymerizing monomers having two or more different fluoroaliphatic groups and two or more different (poly(oxyalkylene))acrylate (or methacrylate), etc. For example, commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), and C6F. 13 Examples include copolymers of acrylate (or methacrylate) having a group and (poly(oxyalkylene))acrylate (or methacrylate), and copolymers of acrylate (or methacrylate) having a C3F7 group, (poly(oxyethylene))acrylate (or methacrylate), and (poly(oxypropylene))acrylate (or methacrylate). Alternatively, surfactants other than fluorine-based and / or silicone-based surfactants as described in paragraph

[0280] of U.S. Patent Application Publication No. 2008 / 0248425 may be used.

[0268] Surfactants (E) may be used individually or in combination of two or more types.

[0269] The composition of the present invention may or may not contain surfactant (E). If the composition of the present invention contains surfactant (E), the content of surfactant (E) is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass, relative to the total solid content of the composition of the present invention.

[0270] <Hydrophobic resin> The composition of the present invention may include a hydrophobic resin (also referred to as "hydrophobic resin (F)"). Hydrophobic resin (F) is a hydrophobic resin different from resins (A) and (B) mentioned above. The hydrophobic resin (F) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups within its molecule and does not need to contribute to the uniform mixing of polar and nonpolar substances. The effects of adding a hydrophobic resin (F) include controlling the static and dynamic contact angles of the resist film surface with respect to water, as well as suppressing outgassing.

[0271] From the viewpoint of uneven distribution on the film surface, the hydrophobic resin (F) preferably has one or more of the following: "fluorine atoms," "silicon atoms," and "CH3 substructures contained in the side chain portion of the resin," and more preferably has two or more. Furthermore, the hydrophobic resin (F) preferably has hydrocarbon groups having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chains.

[0272] If the hydrophobic resin (F) contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chains.

[0273] When the hydrophobic resin (F) contains a fluorine atom, the fluorine atom-containing substructure is preferably an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl group containing a fluorine atom. A fluorine-containing alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have substituents other than fluorine atoms. A cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have substituents other than a fluorine atom. Examples of aryl groups having a fluorine atom include phenyl groups and naphthyl groups, in which at least one hydrogen atom of an aryl group is substituted with a fluorine atom, and they may also have substituents other than fluorine atoms. Examples of repeating units having fluorine or silicon atoms are given in paragraph 0519 of US2012 / 0251948.

[0274] Furthermore, as described above, it is also preferable that the hydrophobic resin (F) has a CH3 substructure in its side chain portion. Here, the CH3 substructures in the side chain portion of the hydrophobic resin include CH3 substructures having ethyl groups and propyl groups, etc. On the other hand, methyl groups directly bonded to the main chain of the hydrophobic resin (F) (for example, α-methyl groups of repeating units having a methacrylic acid structure) are not included in the CH3 substructure in this invention because their contribution to the surface segregation of the hydrophobic resin (F) is small due to the influence of the main chain.

[0275] With regard to hydrophobic resins (F), refer to paragraphs 0348 to 0415 of Japanese Patent Publication No. 2014-010245, and these contents are incorporated herein by reference.

[0276] Furthermore, as the hydrophobic resin (F), resins described in Japanese Patent Publication No. 2011-248019, Japanese Patent Publication No. 2010-175859, and Japanese Patent Publication No. 2012-032544 can also be preferably used.

[0277] The composition of the present invention may or may not contain a hydrophobic resin (F). If the composition of the present invention contains a hydrophobic resin (F), the content of the hydrophobic resin (F) is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% by mass, relative to the total solid content of the composition of the present invention.

[0278] <Other ingredients> The composition of the present invention may contain other components besides those described above. Examples of other components include crosslinking agents, alkali-soluble resins, dissolution inhibitors, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in developing solutions.

[0279] The solid content concentration of the composition of the present invention is 15% by mass or more. This value allows for suitable use as a resist composition for thick films. For the effects of the present invention to be superior, the solid content concentration of the composition of the present invention is preferably 20% by mass or more, and particularly preferably 20 to 45% by mass. The solid content concentration refers to the mass percentage of the mass of the other components (components that can constitute a photosensitive or radiation-sensitive film) excluding the solvent, relative to the total mass of the photosensitive or radiation-sensitive resin composition.

[0280] <Viscosity> The viscosity of the composition of the present invention is not particularly limited, but is preferably 10 to 100 mPa·s, more preferably 15 to 90 mPa·s, and even more preferably 30 to 70 mPa·s at 25°C. The viscosity of the photosensitive or radiation-sensitive resin composition is determined by measuring it at 25°C using an E-type viscometer (RE-85L model, manufactured by Toki Sangyo Co., Ltd.).

[0281] <Preparation method> The composition of the present invention can be prepared by dissolving the aforementioned resin (A), resin (B), and photoacid generator (C), as well as each of the aforementioned components as needed, in a solvent (preferably the aforementioned solvent), and filtering the mixture. The pore size of the filter used for filter filtration is not particularly limited, but is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. In some cases, the pore size of the filter is also preferably 0.1 μm or less, preferably 0.05 μm or less, and preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (JP 2002-62667), cyclic filtration may be performed, or multiple types of filters may be connected in series or parallel for filtration. The composition may also be filtered multiple times. Furthermore, the composition may be subjected to degassing treatment or the like before or after filter filtration.

[0282] <Application> The compositions of the present invention react and change properties upon irradiation with active light or radiation. The compositions of the present invention can be used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit boards such as liquid crystals or thermal heads, fabrication of imprint mold structures, other photofabrication processes, or manufacturing of lithographic printing plates or acid-curable compositions. Patterns formed using the compositions of the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, redistribution formation processes, and MEMS (Micro Electro Mechanical Systems), etc.

[0283] [Pattern formation method, photosensitive or radiation-sensitive film] The pattern forming method of the present invention is The process involves forming a photosensitive or radiation-sensitive film (preferably a resist film) on a substrate using the aforementioned photosensitive or radiation-sensitive resin composition of the present invention, The process of exposing the above-mentioned photosensitive or radiation-sensitive film to obtain an exposed photosensitive or radiation-sensitive film, The process includes the step of developing the exposed photosensitive or radiation-sensitive film using a developing solution to form a pattern. The following details each step.

[0284] (Step a: Actinic ray-sensitive or radiation-sensitive film formation step) Step a is a step of forming an active photosensitive or radiation-sensitive film on a substrate using the composition of the present invention. A method for forming a photosensitive or radiation-sensitive film on a substrate using the composition of the present invention includes coating the substrate with the composition of the present invention. The composition of the present invention can be applied to a substrate (e.g., silicon, silicon dioxide coated) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. Spin coating using a spinner is preferred as the coating method. After applying the composition of the present invention, the substrate may be dried to form a photosensitive or radiation-sensitive film. If necessary, various undercoats (inorganic films, organic films, or anti-reflective films) may be formed beneath the photosensitive or radiation-sensitive film.

[0285] One drying method is heating (pre-baking: PB). Heating can be done using the means provided in a standard exposure machine and / or developing machine, or it may be done using a hot plate or the like. The heating temperature is preferably 80 to 150°C, and more preferably 80 to 140°C. The heating time is preferably 30 to 1000 seconds, and more preferably 40 to 800 seconds.

[0286] The thickness of the photosensitive or radiation-sensitive film is not particularly limited. When the photosensitive or radiation-sensitive film is a photosensitive or radiation-sensitive film for KrF exposure, the film thickness is preferably 5 μm or more, more preferably 5 μm to 30 μm, and even more preferably 7 μm to 15 μm. When the photosensitive or radiation-sensitive film is a resist film for ArF exposure or EUV exposure, the film thickness is preferably 10 to 700 nm, and more preferably 20 to 400 nm. The present invention also relates to photosensitive or radiation-sensitive films formed using the composition of the present invention. When the film thickness of the photosensitive or radiation-sensitive film is 500 nm or more, the effect of the present invention, which is that excellent development defects after aging can be reduced, is particularly evident.

[0287] A topcoat may be formed on the upper layer of a photosensitive or radiation-sensitive film using a topcoat composition. Preferably, the topcoat composition can be applied uniformly to the top layer of the photosensitive or radiation-sensitive film without being mixed with it. The thickness of the topcoat is preferably 10 to 200 nm, and more preferably 20 to 100 nm. The top coat is not particularly limited, and conventionally known top coats can be formed by conventionally known methods. For example, a top coat can be formed according to the description in paragraphs 0072 to 0082 of Japanese Patent Application Publication No. 2014-059543.

[0288] (Process b: Exposure process) Step b is a step of exposing an active photosensitive or radiation-sensitive film to obtain an exposed active photosensitive or radiation-sensitive film. Methods of exposure include placing a mask between the light source and the photosensitive or radiation-sensitive film, or directly irradiating the film with active light or radiation without placing a mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and EB (Electron Beam), with KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and EB being preferred. It is particularly preferable that the light source for exposure in step b be KrF.

[0289] It is preferable to perform baking (post-exposure baking: PEB) after exposure and before development. The heating temperature is preferably 80 to 150°C, and more preferably 80 to 140°C. The heating time is preferably 10 to 1000 seconds, and more preferably 10 to 180 seconds. Heating can be performed using the means provided in a standard exposure and / or developing machine, or it may be done using a hot plate or the like. This process is also referred to as post-exposure baking.

[0290] (Process c: Development process) Step c is a step in which the exposed photosensitive or radiation-sensitive film is developed using a developer to form a pattern. Development methods include immersing the substrate in a tank filled with developer solution for a certain period of time (dip method), developing by piling the developer solution onto the substrate surface using surface tension and letting it remain still for a certain period of time (paddle method), spraying the developer solution onto the substrate surface (spray method), and continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). Alternatively, after the developing process, a step may be performed to stop the development process while substituting with another solvent. The development time is not particularly limited as long as it is enough time for the resin in the unexposed areas to dissolve sufficiently, but 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0291] Examples of developing solutions include alkaline developers and organic solvent developers. As the alkaline developer, it is preferable to use an alkaline aqueous solution containing alkali. In particular, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0.

[0292] An organic solvent developer is a developer that contains an organic solvent. Examples of organic solvents used in organic solvent developers include well-known organic solvents such as ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0293] (Other processes) The pattern forming method of the present invention may include a step of washing with a rinsing solution after step c described above. Examples of rinsing solutions used in the rinsing step after the development process using an alkaline developer include pure water. A suitable amount of surfactant may also be added to the rinsing solution.

[0294] The rinsing solution used in the rinsing step after the development step using an organic developer 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. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. A suitable amount of surfactant may be added to the rinsing solution.

[0295] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate. In other words, the pattern formed in step c may be used as a mask to process the substrate (or the underlying film and the substrate) to form a pattern on the substrate. The processing method for the substrate (or the underlying film and substrate) is not particularly limited, but a preferred method is to form a pattern on the substrate by performing dry etching on the substrate (or the underlying film and substrate) using the pattern formed in step c as a mask. Dry etching may consist of a single stage or multiple stages. If the etching consists of multiple stages, each stage may be the same or a different process. Etching can be performed using any known method, and various conditions are determined appropriately according to the type of substrate or application. For example, etching can be performed in accordance with the Proceedings of the International Society for Optical and Photonics (Proc. of SPIE) Vol. 6924, 692420 (2008), Japanese Patent Publication No. 2009-267112, etc. Alternatively, it can be performed in accordance with the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook, Fourth Edition, Published in 2007, Publisher: SEMI Japan". For dry etching, oxygen plasma etching is preferred.

[0296] The various materials used in the present invention (for example, solvents, developers, rinses, anti-reflective film forming compositions, topcoat forming compositions, etc.) are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. Examples of metallic impurities include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Mo, Zr, Pb, Ti, V, W, and Zn.

[0297] One method for removing impurities such as metals from the above-mentioned materials is filtration using a filter. The filter pore size is preferably 0.20 μm or less, more preferably 0.05 μm or less, and even more preferably 0.01 μm or less. Preferred filter materials include fluororesins such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkanes (PFA), polyolefin resins such as polypropylene and polyethylene, and polyamide resins such as nylon 6 and nylon 66. Filters may be pre-washed with an organic solvent. In the filter filtration process, multiple or multiple types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore sizes and / or materials may be combined. Furthermore, various materials may be filtered multiple times, and the process of filtering multiple times may be a recirculation filtration process. As a recirculation filtration process, for example, a method disclosed in Japanese Patent Application Publication No. 2002-62667 is preferred. As a filter, one that reduces the amount of eluted substances, such as the one disclosed in Japanese Patent Publication No. 2016-201426, is preferable. In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. As the adsorbent, known adsorbents can be used, for example, inorganic adsorbents such as silica gel or zeolite, or organic adsorbents such as activated carbon. As a metal adsorbent, for example, one disclosed in Japanese Patent Application Publication No. 2016-206500 can be cited. Furthermore, methods for reducing impurities such as metals contained in the above-mentioned materials include selecting raw materials with low metal content as constituent materials for the various materials, performing filter filtration on the constituent materials, or performing distillation under conditions that suppress contamination as much as possible by lining or coating the inside of the apparatus with fluororesin or the like. The preferred conditions for filter filtration performed on the constituent materials are the same as those described above. The above materials are preferably stored in containers as described in U.S. Patent Application Publication No. 2015 / 0227049, Japanese Patent Publication No. 2015-123351, Japanese Patent Publication No. 2017-13804, etc., in order to prevent contamination with impurities. Various materials may be diluted with the solvent used in the composition before use.

[0298] Furthermore, the present invention also relates to a method for manufacturing an electronic device, including the pattern formation method described above. The electronic device of the present invention is preferably mounted on electrical and electronic equipment (such as home appliances, office automation (OA) equipment, media-related equipment, optical equipment, and communication equipment). [Examples]

[0299] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. The scope of the present invention shall not be construed as being limited by the following examples.

[0300] <Resin (A)> The following resins A-1 to A-5 were used as resin (A). Table 1 shows the composition of A-1 to A-5 (type of repeating unit, composition ratio of repeating units (mol% ratio), weight-average molecular weight (Mw), and degree of dispersion (Mw / Mn)). The number-average molecular weight (Mn), weight-average molecular weight (Mw), and degree of dispersion (molecular weight distribution (Mw / Mn)) of each resin were measured by the method described above. Furthermore, the composition ratio (in mole%) of repeating units in each resin was determined as follows: 13 The measurement was performed using 1C-NMR (nuclear magnetic resonance).

[0301] [Table 1]

[0302] In the resins A-1 to A-5 in Table 1 above, the repeating units are as follows:

[0303] [ka]

[0304] <Resin (B)> The following resins B-1 to B-25 were used as resin (B). The number-average molecular weight (Mn), weight-average molecular weight (Mw), and degree of dispersion (molecular weight distribution (Mw / Mn)) of each resin were measured by the method described above. Furthermore, the composition ratio (in mole%) of repeating units in each resin was determined as follows: 13 The measurement was performed using 1C-NMR (nuclear magnetic resonance). Resins B-1X to B-5X are not resin (B), but are listed for convenience.

[0305] [Table 2]

[0306] In Table 2 above, the repeating units for resins B-1 to B-25 and B-1X to B-5X are as follows: Furthermore, for mB1-1 to mB1-11 and mB3-2, the sum of the atomic weights of the atoms constituting the -(AL-Y-)n-R2 site is also shown.

[0307] [ka]

[0308] [ka]

[0309] [ka]

[0310] In Table 2, in Repeating Unit 1, Repeating Units mB1-1 to mB1-11 each correspond to Repeating Unit (b1). In repeating unit 1, repeating units mB1-10 and mB1-11 correspond to repeating unit (b1) and also to repeating unit (b2).

[0311] The above resin was synthesized by radical polymerization.

[0312] <Photoacid Generator (C)> The structure of the compound used as a photoacid generator is shown below.

[0313] [ka]

[0314] <Acid diffusion control agent> The structure of the compound used as an acid diffusion control agent is shown below.

[0315] [ka]

[0316] <Solvent> The solvents used are listed below. PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether nBA: Butyl acetate

[0317] <Preparation of the resist composition> The components shown in Table 3 below were dissolved in the solvents shown in the same table to prepare solutions with the solid content concentrations shown in the same table. These solutions were then filtered through a polyethylene filter with a pore size of 3 μm to obtain resist compositions R-1 to R-40 and RX-1 to RX-5. Note that "solid content" refers to all components other than the solvent. The obtained resist composition was used in the examples and comparative examples. The content of each component (excluding the solvent) in Table 3 is expressed in parts by mass. The solid content concentration represents the mass percentage of the mass of the components other than the solvent relative to the total mass of each resist composition. The solvents used were the compounds shown in Table 3, in the mass ratios shown in Table 3. The content of resin (B) per 100 parts by mass of resin (A) is shown in Table 3 as "resin (B) / resin (A)". The content of compound (C) per 100 parts by mass of resin (B) is shown in Table 3 as "Compound (C) / Resin (B)".

[0318] [Table 3]

[0319] [Table 4]

[0320] <Pattern formation> Using a Tokyo Electron ACT-8 spin coater, the resist composition prepared above was applied to a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane, without the application of an anti-reflective layer. The substrate was then heated and dried at 150°C for 60 seconds to form a 10 μm thick photosensitive or radiation-sensitive film (resist film). This resist film was pattern-exposed using a KrF excimer laser scanner (ASML, PAS5500 / 850C, wavelength 248 nm) under exposure conditions of NA=0.55 and σ=0.60. After irradiation, the film was baked at 130°C for 60 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and then dried. Exposure was performed through a mask with a line-and-space pattern such that the space pattern after reduction projection exposure was 3 μm and the pitch was 33 μm. The resulting space pattern was 3 μm and the pitch was 33 μm. The width of the space pattern was measured using a scanning electron microscope (SEM) (Hitachi 9380). An evaluation pattern wafer having a substrate and a pattern formed on the substrate surface was obtained by the above procedure.

[0321] The crack resistance and defects over time were evaluated as follows.

[0322] <Crack Resistance> The evaluation pattern wafer was subjected to a 60-second vacuum treatment in a chamber within a SEM (Hitachi 9380). The pressure inside the chamber was set to 0.002 Pa. After vacuum treatment, the evaluation pattern wafers were observed using an optical microscope to assess the presence or absence of cracks. Specifically, cracks in the patterns formed on the substrate surface were checked and evaluated based on the following criteria. A: No cracks B: 1 to 3 cracks C: 3 to 5 cracks D: 6 or more cracks

[0323] <Evaluation of defects over time (time-dependent defects)> Using a resist composition prepared within 3 days (stored at room temperature (25°C)), isolated patterns with a thickness of 10 μm were formed (space pattern of 3 μm, pitch of 33 μm). The total number of defects in the wafer (total number of defects) was measured for the obtained patterns using a surface defect observation device (KLA-Tencor, product name: KLA2360). Two wafers were used for each example, and the average value was adopted as the "initial number of defects". Subsequently, the resist composition was stored at room temperature for 6 months, and then a resist pattern was formed in the same manner. The same evaluation as above was performed, and the "number of defects after aging" was measured. The temporal stability of the number of defects was evaluated according to the following criteria. (Temporal stability of defect count) = (Number of defects after time) - (Initial number of defects) A: Up to 10 B: 10~100 pieces C: 100~1000 pieces D: More than 1000 pieces

[0324] The results obtained are shown in Table 4.

[0325] [Table 5]

[0326] As can be seen from Table 4, the resist compositions of the examples were able to suppress the occurrence of cracks in the pattern while reducing defects in the pattern over time.

Claims

1. The solid content concentration is 15% or more. (A) A resin containing a repeating unit (a1) having an acid-degradable group and a repeating unit (a2) having an aromatic ring. (B) A resin containing a repeating unit (b1) represented by the following general formula (1) (C) Compounds that generate acid upon irradiation with active light or radiation. A photosensitive or radiation-sensitive resin composition containing, A photosensitive or radiation-sensitive resin composition wherein the content of repeating units having acid-degradable groups in the resin (B) is 5 mol% or less relative to the total repeating units in the resin (B). 【Chemistry 1】 In general formula (1), R １ , R ２ Each of these independently represents either a hydrogen atom or a hydrocarbon group. AL represents a linear or branched alkylene group. When n is an integer of 2 or more, multiple ALs may be the same or different. However, AL does not contain an acid-degradable group. Y represents -O-, -S-, -COO-, or -OCO-. If n represents an integer greater than or equal to 2, then multiple values ​​of Y may be the same or different. -(AL-Y-)n-R ２ The sum of the atomic weights of the atoms that make up the part is 70 or more. n represents an integer greater than or equal to 1.

2. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (B) substantially does not contain fluorine atoms and silicon atoms.

3. -(AL-Y-)n-R ２ The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the sum of the atomic weights of the atoms constituting the part is 80 or more.

4. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein n in the general formula (1) is an integer of 2 or more.

5. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (b1) is a repeating unit represented by the following general formula (2). 【Chemistry 2】 In general formula (2), R １ , R ２ Each of these independently represents either a hydrogen atom or a hydrocarbon group. AL represents a linear or branched alkylene group. When n is an integer of 2 or more, multiple ALs may be the same or different. However, AL does not contain an acid-degradable group. -(AL-O-)n-R ２ The sum of the atomic weights of the atoms that make up the part is 70 or more. n represents an integer greater than or equal to 1.

6. The photosensitive or radiation-sensitive resin composition according to claim 5, wherein the repeating unit (b1) is a repeating unit represented by the following general formula (3). 【Transformation 3】 In general formula (3), R １ and R ２ each independently represents a hydrogen atom or a hydrocarbon group. - (CH ２ CH ２ -O-)n-R ２ The sum of the atomic weights of the atoms that make up the part is 70 or more. n represents an integer greater than or equal to 1.

7. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (B) comprises a repeating unit (b2) having a carboxyl group or a hydroxyl group.

8. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the content of resin (B) is 40 parts by mass or less per 100 parts by mass of resin (A).

9. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the molar content of the repeating units (b1) contained in the resin (B) is 25 mol% or more relative to the total repeating units in the resin (B).

10. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the content of compound (C) contained in the composition is 3 to 20 parts by mass per 100 parts by mass of resin (B).

11. A photosensitive or radiation-sensitive film formed from a photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 10.

12. A pattern forming method comprising the steps of: forming an active photosensitive or radiation-sensitive film on a substrate using an active photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 10; exposing the active photosensitive or radiation-sensitive film; and developing the exposed active photosensitive or radiation-sensitive film using a developer to form a pattern.

13. A method for manufacturing an electronic device, comprising the pattern forming method described in claim 12.

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