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

Abstract

This invention provides a photosensitive radioactive or radioactive linear resin composition capable of producing patterns with excellent LWR performance, a resist film, a pattern forming method, a method for manufacturing electronic devices, a compound, and a method for manufacturing the compound. The photosensitive radioactive or radioactive linear resin composition of this invention comprises a resin having repeating units containing groups whose polarity increases through acid decomposition. In addition to the resin, the photosensitive radioactive or radioactive linear resin composition further comprises a compound having at least one cation represented by general formula (1), or the resin, in addition to the repeating units, has repeating units containing cations represented by general formula (1). (R) d1 ) m -[X d1 ] + -(L d1 -Ar d1 -(S-X) d2 ) p ) n (1)

Description

Technical Field

[0001] This invention relates to a photosensitive radioactive or radiosensitive linear resin composition, a patterning method, a resist film, a method for manufacturing electronic devices, a compound, and a method for manufacturing the compound. Background Technology

[0002] In the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), micro-processing is performed using photolithography with photosensitive compositions.

[0003] As a photolithography method, one example is the method of forming a resist film by means of a photosensitive composition, exposing the obtained film, and then developing it.

[0004] In Patent Document 1, specified compounds are disclosed as acid-generating agents for use in photosensitizing compositions, for example, the following compounds are exemplified.

[0005] [Chemical Formula 1]

[0006]

[0007] Previous technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2009-019028 Summary of the Invention

[0010] The technical problem to be solved by the invention

[0011] The inventors conducted a detailed study on the properties of the compounds disclosed in Patent Document 1, and found that the photosensitive radioactive or radiolinear resin composition containing the compounds described in Patent Document 1 has room for improvement in the LWR (line width roughness) performance of the obtained pattern.

[0012] Therefore, the objective of this invention is to provide a photosensitive radioactive or radiosensitive linear resin composition that can produce patterns with excellent LWR performance.

[0013] Furthermore, the present invention also aims to provide a resist film, a patterning method, a method for manufacturing electronic devices, a compound, and a method for manufacturing the compound in relation to the above-mentioned photosensitive or radiosensitive linear resin composition.

[0014] means for solving technical problems

[0015] The inventors have discovered that the above-mentioned problems can be solved by the following structure.

[0016] (1) A photosensitive radioactive or radiosensitive linear resin composition comprising a resin having repeating units containing groups whose polarity increases through acid decomposition.

[0017] The photosensitive or radiosensitive linear resin composition, in addition to the resin, comprises a compound having at least one cation represented by the general formula (1) described below, or

[0018] In addition to the repeating units, the resin also has repeating units containing cations represented by the general formula (1) described later.

[0019] (2) The photosensitive radioactive or radiosensitive linear resin composition according to (1), wherein,

[0020] The photosensitive or radiosensitive linear resin composition comprises a compound having at least one cation represented by general formula (1).

[0021] A compound having at least one cation represented by general formula (1) comprises at least one selected from compounds represented by general formula (2) and compounds represented by general formula (3) described below.

[0022] (3) The photosensitive radioactive or radiosensitive linear resin composition according to (1) or (2), wherein,

[0023] X d1 It is a sulfur atom.

[0024] (4) The photosensitive radioactive or radiosensitive linear resin composition according to any one of (1) to (3), wherein,

[0025] In general formula (1), the group whose polarity increases due to decomposition by the action of acid is the group represented by general formula (a-1) described later.

[0026] (5) The photosensitive radioactive or radiosensitive linear resin composition according to any one of (1) to (4), wherein,

[0027] In general formula (1), n ​​represents an integer from 2 to 3 or p represents an integer from 2 to 5.

[0028] (6) A resist film formed using any one of (1) to (5) a photosensitive or radiosensitive linear resin composition.

[0029] (7) A pattern forming method comprising the following steps:

[0030] The process of forming a resist film on a substrate using any one of (1) to (5);

[0031] The process of exposing a photoresist film; and

[0032] The process of developing an exposed resist film using a developer to form a pattern.

[0033] (8) A method for manufacturing an electronic device, comprising the pattern forming method described in (7).

[0034] (9) A compound having at least one cation represented by the general formula (1) described below.

[0035] (10) The compound according to (9) is a compound represented by general formula (2) or general formula (3) described below.

[0036] (11) The compound according to (9) or (10), wherein,

[0037] X d1 It is a sulfur atom.

[0038] (12) The compound according to any one of (9) to (11), wherein,

[0039] In general formula (1), the group whose polarity increases due to decomposition by the action of acid is the group represented by general formula (a-1) described later.

[0040] (13) The compound according to any one of (9) to (12), wherein,

[0041] In general formula (1), n ​​is an integer from 2 to 3 or p is an integer from 2 to 5.

[0042] (14) A method for manufacturing a compound having at least one cation represented by general formula (1) as described in any one of (9) to (13), wherein in the method for manufacturing the compound,

[0043] In the presence of an alkaline compound, a compound having at least one cation represented by general formula (4) described later is reacted with a compound represented by general formula (5) described later, thereby producing a compound having at least one cation represented by general formula (1).

[0044] Invention Effects

[0045] According to the present invention, a photosensitive radioactive or radiosensitive linear resin composition that can produce patterns with excellent LWR performance can be provided.

[0046] Furthermore, according to the present invention, it is possible to provide a resist film, a pattern forming method, a method for manufacturing electronic devices, a compound, and a method for manufacturing compounds related to the above-mentioned photosensitive or radiosensitive linear resin composition. Detailed Implementation

[0047] Hereinafter, an example of a method for implementing the present invention will be described.

[0048] The numerical range indicated by “~” in this specification refers to the range including the values ​​recorded before and after “~” as the lower and upper limits.

[0049] In this specification, the designations of groups (atomic groups) that do not specify whether they are substituted or unsubstituted include both substituted groups and unsubstituted groups. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0050] Unless otherwise stated, the substituent is preferably a monovalent substituent.

[0051] In this specification, "organic group" refers to a group containing at least 10 carbon atoms.

[0052] In this specification, examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0053] Unless otherwise stated, the bonding direction of the divalent groups marked in this specification is not limited. For example, when Y in a compound represented by the general formula "XYZ" is -COO-, Y can be -CO-O- or -O-CO-. Furthermore, the above compound can be "X-CO-OZ" or "XO-CO-Z".

[0054] In this specification, "(meth)acrylic acid" is a general term encompassing acrylic acid and methacrylic acid, specifically referring to "at least one of acrylic acid and methacrylic acid". Similarly, "(meth)acrylic acid" refers to "at least one of acrylic acid and methacrylic acid".

[0055] In this manual, "photochemical rays" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this manual, "light" refers to photochemical rays or radiation.

[0056] Unless otherwise stated, “exposure” in this specification includes not only exposure using bright-line spectra of mercury lamps, far-ultraviolet light represented by excimer lasers (ArF excimer lasers, etc.), X-rays and EUV light, but also depictions using particle beams such as electron beams and ion beams.

[0057] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (hereinafter also referred to as "molecular weight distribution") of the resin in this specification are defined as polystyrene conversion values ​​determined by GPC using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 °C, flow rate: 1.0 mL / min, detector: refractive index detector).

[0058] 1×10 -10 m.

[0059] The acid dissociation constant (pKa) in this specification refers to the pKa in aqueous solution, specifically, a value calculated using software package 1 described below, based on a database of Hammett substituent constants and known literature values. All pKa values ​​described in this specification are values ​​calculated using this software package.

[0060] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007ACD / Labs).

[0061] On the other hand, pKa can also be determined using molecular orbital algorithms. Specifically, this can be exemplified by calculating H in the solvent based on thermodynamic cycles. + The method for calculating the dissociation free energy. (In addition, water is usually used as the solvent mentioned above in this specification; DMSO (dimethyl sulfoxide) is used when water cannot be used to determine the pKa.)

[0062] Regarding H +Methods for calculating the dissociation free energy include, for example, the DFT (density functional method), but various other methods have been reported in the literature and are not limited to this. Furthermore, several software programs exist capable of implementing the DFT, such as Gaussian16.

[0063] As mentioned above, pKa in this specification refers to the value obtained by using software package 1 to calculate a database of substituent constants based on Hammett and known literature values. However, when pKa cannot be calculated by this method, the value obtained by Gaussian16 based on DFT (density functional method) is used.

[0064] [Photosensitive X-ray or radiosensitive linear resin composition]

[0065] The photosensitive or radiosensitive linear resin composition of the present invention (hereinafter also referred to as "resist composition") will be described.

[0066] The resist composition of the present invention can be a positive resist composition or a negative resist composition. Furthermore, it can be a resist composition for alkaline development or a resist composition for organic solvent development.

[0067] The compositions of the present invention are typically chemically amplified resist compositions.

[0068] The resist composition of the present invention is a resist composition comprising a resin (hereinafter also referred to as an "acid-degradable resin") containing repeating units having groups whose polarity increases through acid decomposition (hereinafter also referred to as "repeating units having acid-degradable groups"). The resist composition, in addition to the acid-degradable resin, also comprises a compound (hereinafter also referred to as a "specific compound") having at least one cation represented by the general formula (1) described below, or the acid-degradable resin, in addition to the repeating units having acid-degradable groups, also comprises repeating units having cations represented by the general formula (1) described below (hereinafter also referred to as "specific repeating units").

[0069] In other words, the resist composition of the present invention comprises an acid-degradable resin and a specific compound or comprises an acid-degradable resin having a specific repeating unit.

[0070] Although the mechanism by which this structure solves the problem of the present invention is not yet clear, it is speculated as follows. Furthermore, the following explanation uses a specific compound as an example.

[0071] Specific compounds are commonly used as photoacid generators. Because these compounds contain sulfur atoms at designated positions, the polarity of the cations is lower than that of the compounds described in Patent Document 1. This suppresses aggregation of the specific compounds and enhances their compatibility with acid-degradable resins, resulting in excellent LWR performance for the formed patterns. In particular, the acid-degradable groups in the specific compounds decompose together with the polar groups generated by the acid-degradable resin to produce polar groups. This leads to increased solubility of the exposure section in alkaline developers and decreased solubility in organic solvent developers, resulting in improved LWR performance in both positive and negative patterns.

[0072] Hereinafter, in this specification, the situation in which a pattern with superior LWR performance can be obtained will also be referred to as the superior effect of the present invention.

[0073] [Resistant Composition]

[0074] The following is a detailed description of the components that may be contained in an anti-corrosion composition.

[0075] <Compounds having at least one cation represented by general formula (1)>

[0076] The resist compositions of the present invention comprise specific compounds or acid-degradable resins having specific repeating units described later. Hereinafter, the specific compounds will be described in detail first.

[0077] Specific compounds function as photoacid generators or acid diffusion inhibitors. Photoacid generators are compounds that produce acid upon irradiation (exposure) by photochemical rays or radiation (preferably EUV or ArF). Acid diffusion inhibitors function as quenchers that capture the acid produced by photoacid generators; they are compounds that control the diffusion of acid within the resist film.

[0078] When a specific compound functions as a photoacid generator, there are no particular limitations; the pKa of the acid produced by the specific compound is generally lower than the pKa of the acid produced by the acid diffusion control agent described later in the resist composition. When a specific compound functions as a photoacid generator, it is generally able to decompose the acid-degrading resin described later through the action of acid.

[0079] When a specific compound functions as an acid diffusion controller, there are no particular limitations; the pKa of the acid produced by the specific compound is generally greater than the pKa of the acid produced by the photoacid generator contained alone in the resist composition. When a specific compound functions as an acid diffusion controller, it is generally impossible to decompose the acid-degradable resin described below by the action of acid.

[0080] That is, a particular compound can function as a photoacid generator or an acid diffusion control agent depending on its relationship with other components contained in the resist composition.

[0081] The volume of acid produced by a specific compound is not particularly limited, but from the viewpoint of suppressing the diffusion of acid generated during exposure into the non-exposed areas and improving resolution, it is preferable to... The above, better The above further optimizes The above are particularly preferred. That's all. Furthermore, from the viewpoint of sensitivity or solubility in the coating solvent, the volume of acid produced by the specific compound is preferably... The following is preferred The following are further optimizations. the following.

[0082] The volume values ​​mentioned above were obtained using "WinMOPAC" manufactured by Fujitsu Limited. In calculating these volumes, the chemical structures of the acids involved in each example were first input. Then, using this structure as the initial structure, molecular force field calculations using the MM (Molecular Mechanics) method were performed to determine the most stable stereocoordinates of each acid. Subsequently, molecular orbital calculations using the PM (Parameterized Model number) method were performed on these most stable stereocoordinates, thereby allowing the calculation of the "accessible volume" of each acid.

[0083] The specific compound is preferably a compound that produces an acid (preferably an organic acid) by exposure.

[0084] Examples of the aforementioned acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acid, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonyl sulfonyl imine acids, bis(alkyl sulfonyl) imine acids, and tri(alkyl sulfonyl) methylated acids, etc.

[0085] The structure of the acid produced by a specific compound is not particularly limited. However, from the viewpoint of suppressing acid diffusion and improving resolution, it is preferable that the acid produced by the specific compound has a strong interaction with the acid-degrading resin described later. From this perspective, when the acid produced by the photoacid generator is an organic acid, it is preferable that the organic acid has polar groups in addition to organic acid groups such as sulfonic acid groups, carboxylic acid groups, carbonyl sulfonyl imide groups, disulfonyl imide groups, and trisulfonyl methyl acid groups.

[0086] Examples of polar groups include ether, ester, amide, acyl, sulfonyl, sulfonyloxy, sulfonamide, thioether, thioester, urea, carbonate, carbamate, hydroxyl, and mercapto.

[0087] The number of polar groups in the generated acid is not particularly limited, but it is preferably one or more, more preferably two or more. However, from the viewpoint of suppressing excessive development, the number of polar groups is preferably less than six, more preferably less than four.

[0088] The specific compound is a compound having at least one cation represented by the general formula (1).

[0089] There is no particular limitation on the number of cations represented by general formula (1) in a specific compound, as long as there is one or more, or two or more.

[0090] When a particular compound has two or more cations represented by general formula (1), the number is preferably two to three.

[0091] [Chemical Formula 2]

[0092] (R d1 ) m -[X d1 ] + -(L d1 -Ar d1 -(SX d2 ) p ) n (1)

[0094] In general formula (1), X d1 It represents a sulfur atom or an iodine atom.

[0095] From the viewpoint of the superior effects of the present invention, X d1 The preferred atom is sulfur.

[0096] When X d1 When representing a sulfur atom, n represents an integer from 1 to 3, m represents an integer from 0 to 2, and m+n equals 3. When X d1 When representing an iodine atom, n represents 1 or 2, m represents 0 or 1, and m+n is 2.

[0097] p represents an integer from 1 to 5.

[0098] From the viewpoint of achieving excellent results in this invention, p is preferably an integer from 1 to 4, more preferably an integer from 1 to 3, and even more preferably 1.

[0099] In addition, when n is 2 or more, multiple p can be the same or different.

[0100] Furthermore, from the viewpoint of achieving better results in this invention, n is preferably 2 to 3 or p is preferably 2 to 5, and n is more preferably 2 to 3 or p is more preferably 2 to 3.

[0101] R d1This indicates a linear, branched, or cyclic alkyl group that may have substituents, a linear, branched, or cyclic alkenyl group that may have substituents, or an aryl group that may have substituents.

[0102] Among them, R d1 Preferably, it is a linear, branched, or cyclic alkyl group that may have substituents, or an aryl group that may have substituents, more preferably an aryl group that may have substituents.

[0103] By R d1 The aryl group, which may have substituents, can be monocyclic or polycyclic. Preferably, the aryl group is monocyclic. Furthermore, the alkyl or alkenyl group is preferably cyclic.

[0104] R d1 It can have substituents or be unsubstituted.

[0105] R d1 The substituents are preferably alkyl groups that may have heteroatoms, and more preferably alkyl groups that have at least one selected from oxygen atoms and halogen atoms.

[0106] By R d1 The indicated group preferably has 30 or fewer carbon atoms, more preferably 25 or fewer, and even more preferably 20 or fewer. There is no particular limitation on the lower limit of the number of carbon atoms, but 3 or more is preferred.

[0107] When m represents 2, there are 2 R... d1 They can bond together to form a ring. The ring formed as described above preferably has 5 or 6 ring members. R d1 In the ring formed by mutual bonding, one of the methylene groups constituting the ring can be replaced by a group having heteroatoms such as oxygen atoms or carbonyl groups.

[0108] L d1 Each can be used to independently represent a single bond or a divalent linker.

[0109] From the viewpoint that the present invention has superior effects, L d1 Single bonds are preferred.

[0110] As a result of L d1 The divalent linking group can be represented by, for example, -O-, -CO-, -COO-, -S-, -NH-, CS-, -SO-, -SO2-, a hydrocarbon group that may have substituents (e.g., alkylene, cycloalkylene, alkenyl, and arylene), and a linking group formed by linking multiple of them.

[0111] The divalent linker preferably has a hydrocarbon group that can have substituents, and more preferably has a methylene, ethylene, or propylene group.

[0112] Ard1 This indicates an aromatic hydrocarbon cyclic group that can have substituents.

[0113] The aromatic hydrocarbon cyclic group can be monocyclic or polycyclic. Monocyclic is preferred.

[0114] As a product of Ar d1 The aromatic hydrocarbon cyclic group represented can be, for example, a benzyl group, a naphthyl group, or anthracene group. Preferably, the aromatic hydrocarbon cyclic group is a benzyl group or a naphthyl group, more preferably a benzyl group.

[0115] By Ar d1 The aromatic hydrocarbon cyclogroup indicated may have substituents or be unsubstituted. Preferably, the aromatic hydrocarbon cyclogroup is unsubstituted.

[0116] Examples of substituents for the aforementioned aromatic hydrocarbon cycloalloys include halogen atoms, straight-chain or branched alkyl groups having halogen atoms, and alkoxy groups having halogen atoms. Among these, unsubstituted straight-chain or branched alkyl groups are preferred.

[0117] X d2 This indicates a group represented by general formula (1-1) or a detachable group that is released by the action of an acid. In general formula (1-1), * indicates a bonding position.

[0118] General formula (1-1)*-L d2 -R d2

[0119] In general formula (1-1), L d2 This represents a single bond or a divalent linker. From the viewpoint of superior performance of the present invention, L... d2 The preferred linker is a divalent linker.

[0120] As a result of L d2 The divalent linker can be exemplified by the L mentioned above. d1 The illustrated divalent linker.

[0121] R d2 This refers to a group whose polarity increases through decomposition by the action of an acid (hereinafter also referred to as an "acid-decomposing group").

[0122] An acid-degradable group is a group that decomposes into a polar group through the action of an acid. Preferably, the acid-degradable group has a structure with a release group protecting the polar group, which is removed by the action of an acid. That is, a specific compound has a group that decomposes into a polar group through the action of an acid. The increased polarity through the action of an acid increases the solubility in alkaline developing solutions while decreasing the solubility in organic solvents.

[0123] As a polar group, an alkaline-soluble group is preferred. Examples of such groups include carboxyl, hydroxyl, phenolic hydroxyl, sulfonic acid, phosphoric acid, sulfonamide, sulfonylimide, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene, and tri(alkylsulfonyl)methylene.

[0124] The polar group is preferably selected from at least one of carboxyl, hydroxyl, phenolic hydroxyl and sulfonic acid groups, and more preferably carboxyl, hydroxyl or phenolic hydroxyl.

[0125] As a detaching group that is released by the action of an acid, examples include groups represented by general formulas (S1) to (S3).

[0126] General formula (S1): -C(Rx) S1 (Rx) S2 (Rx) S3 )

[0127] General formula (S2): -C(=O)OC(Rx) S1 (Rx) S2 (Rx) S3 )

[0128] General formula (S3): -C(R) S1 (R) S2 (OR) S3 )

[0129] In general formulas (S1) and (S2), Rx S1 ~Rx s3 Each can be independently represented as a straight-chain or branched alkyl group that may have substituents, a cycloalkyl group (monocyclic or polycyclic) that may have substituents, or an aryl group (monocyclic or polycyclic) that may have substituents.

[0130] Among them, Rx S1 ~Rx S3 Preferably, each Rx is a straight-chain or branched alkyl group that may have substituents. s1 ~Rx S3 More preferably, each is a straight-chain alkyl group that may have substituents.

[0131] Rx S1 ~Rx S3 Two of them can also bond together to form a single ring or multiple rings.

[0132] As Rx S1 ~Rx S3The alkyl group is preferably an alkyl group with 1 to 10 carbon atoms, such as tert-butyl, tert-heptyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.

[0133] As for the cycloalkyl groups Rx1 to Rx3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl.

[0134] As Rx S1 ~Rx S3 The ring formed by the two bonds in Rx is preferably a cycloalkyl group. S1 ~Rx S3 The cycloalkyl group formed by the bonding of two atoms is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl or adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0135] Rx S1 ~Rx S3 In the cycloalkyl group formed by the two bonds, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom other than a fluorine atom, or a group having a heteroatom other than a fluorine atom such as a carbonyl group.

[0136] In general formula (S3), R S1 ~R S3 Each can be used independently to represent a hydrogen atom or a monovalent organic group. R S2 ~R S3 They can bond with each other to form a ring. Examples of monovalent organic groups include straight-chain or branched alkyl groups that can have substituents, and cycloalkyl groups that can have substituents. As R S1 It can also be chosen as a hydrogen atom.

[0137] Furthermore, the aforementioned alkyl and cycloalkyl groups may also contain groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups. For example, in the aforementioned alkyl and cycloalkyl groups, one or more of the methylene groups may be substituted with groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups.

[0138] Furthermore, R S3 It can bond with another substituent in the main chain of the repeating unit to form a ring.

[0139] As an acid-decomposing group, it is preferably a group represented by general formulas (a-1) to (a-5), more preferably a group represented by general formula (a-1) or (a-2), and even more preferably a group represented by general formula (a-1).

[0140] [Chemical Formula 3]

[0141]

[0142] In general formula (a-1), R a1 This indicates a detached radical that is released by the action of an acid. * indicates a bonding position.

[0143] Examples of detachable groups that are released by the action of acid include the groups represented by the general formulas (S1) to (S3).

[0144] Among them, R a1 Preferably, it refers to a straight-chain or branched alkyl group that may have substituents, or a cycloalkyl group that may have substituents.

[0145] From the viewpoint that the present invention offers superior performance, R a1 The alkyl group represented is either straight-chain or branched and may have substituents, preferably a branched alkyl group that may have substituents.

[0146] The aforementioned alkyl group can be a straight-chain or branched alkyl group with substituents, or an unsubstituted straight-chain or branched alkyl group. The substituents in the aforementioned alkyl group are preferably heteroatoms such as oxygen atoms or alkyl groups containing heteroatoms such as oxygen atoms. From the viewpoint of better performance of the present invention, unsubstituted straight-chain or branched alkyl groups are preferred.

[0147] The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 2 to 10, and even more preferably 2 to 8.

[0148] As a result of R a1 Alkyl groups, for example, include tert-butyl, tert-heptyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, 1-methylheptyl, and 2-ethylhexyl.

[0149] From the viewpoint that the present invention has superior effects, R a1 The alkyl group represented is preferably tert-butyl or tert-heptyl.

[0150] By R a1 The cycloalkyl group represented can be monocyclic or polycyclic.

[0151] The aforementioned cycloalkyl group can be a substituted cycloalkyl group or an unsubstituted cycloalkyl group. Preferably, it is a substituted cycloalkyl group.

[0152] Examples of substituents that can be found in the aforementioned cycloalkyl groups include alkyl groups and aryl groups that can have substituents.

[0153] Preferably, the alkyl group has 1 to 6 carbon atoms or may have a substituent aryl group, more preferably methyl or ethyl.

[0154] The number of carbon atoms in the above-mentioned cycloalkyl group is preferably 4 to 25, more preferably 4 to 20, and even more preferably 4 to 15.

[0155] As a result of R a1 Examples of cycloalkyl groups include cyclopentyl groups such as methylcyclopentyl or ethylcyclopentyl, cyclohexyl groups such as methylcyclohexyl or ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl, tricyclodecyl, tetracyclododecyl, and adamantyl groups such as methyladamantyl or ethyladamantyl.

[0156] From the viewpoint that the present invention has superior effects, R a1 The cycloalkyl group represented is preferably at least one selected from cyclopentyl, cyclohexyl, cycloheptyl and adamantyl, more preferably methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl or ethyladamantyl.

[0157] [Chemical Formula 4]

[0158]

[0159] In general formula (a-2), * denotes the bonding site. R a2 This indicates a straight-chain or branched alkyl group that may have substituents, or a cycloalkyl group that may have substituents.

[0160] As a result of R a2 The term "alkyl group" can refer to a straight-chain or branched alkyl group that may have substituents, and its meaning is the same as that of the alkyl group described above. a1 The same applies to straight-chain or branched alkyl groups that can have substituents.

[0161] As a result of R a2 The term can refer to cycloalkyl groups that may have substituents, for example, the cycloalkyl groups mentioned above composed of R... a1 This indicates a cycloalkyl group that may have substituents.

[0162] R a3 It represents a hydrogen atom, a straight-chain or branched alkyl group that may have substituents, or a cycloalkyl group that may have substituents.

[0163] As a result of R a3 The term "alkyl group" can refer to a straight-chain or branched alkyl group that may have substituents, and its meaning is the same as that of the alkyl group described above. a1 The same applies to straight-chain or branched alkyl groups that can have substituents.

[0164] As a result of R a3The term "cycloalkyl group" indicates that it may have substituents, and its meaning is the same as that of the group described above, represented by R. a1 The same applies to cycloalkyl groups that can have substituents.

[0165] R a2 and R a3 They can bond together to form a ring.

[0166] R a2 and R a3 The rings formed by bonding together can be single rings or multiple rings. Among them, single rings are preferred.

[0167] As R a2 and R a3 Monocyclic rings formed by bonding together can include, for example, cycloalkanes with 3 to 6 carbon atoms. More specifically, examples include cyclopropane, cyclobutane, cyclopentane, and cyclohexane rings. Some of the carbon atoms in these rings can be replaced by heteroatoms such as oxygen atoms.

[0168] [Chemical Formula 5]

[0169]

[0170] In general formula (a-3), * indicates the bonding position.

[0171] R a4 This refers to a detached radical that is released by the action of an acid.

[0172] Examples of detaching radicals include the groups represented by the general formulas (S1) to (S3) mentioned above.

[0173] [Chemical Formula 6]

[0174]

[0175] In general formula (a-4), * represents the bonding position.

[0176] R a5 and R a6 Each can be used to independently represent a straight-chain or branched alkyl group.

[0177] R a5 and R a6 They can bond with each other to form monocyclic (e.g., aliphatic hydrocarbon rings) or polycyclic rings.

[0178] [Chemical Formula 7]

[0179]

[0180] In general formula (a-5), * indicates the bonding position.

[0181] R a7 and Ra8 Each can be independently represented as a straight-chain or branched alkyl group that may have substituents.

[0182] By X d2 There is no particular limitation on the type of dissociative group that is released by the action of the acid; well-known dissociative groups can be cited. Furthermore, through X... d2 The acid represents the action of the radical to remove the radical from the general formula (1) by -SX. d2 When the indicated group is removed, an SH group (thiol group) is formed.

[0183] Examples of detaching radicals include the groups represented by the general formulas (S1) to (S3) mentioned above.

[0184] (Organic anions)

[0185] The specific compound preferably contains an organic anion.

[0186] As an organic anion, it can be an organic anion with a valence of 1 or 2 or higher. Among them, the organic anion is preferably valenced to 3.

[0187] Organic anions are preferably anions with significantly low ability to induce nucleophilic reactions; specifically, non-nucleophilic anions can be cited.

[0188] Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, and camphor sulfonic acid anions), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions), sulfonyl imide anions, bis(alkylsulfonyl) imide anions, and tri(alkylsulfonyl) methylated anions.

[0189] The aliphatic site in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion can be a straight-chain or branched alkyl group, or a cycloalkyl group. Preferably, it is a straight-chain or branched alkyl group with 1 to 30 carbon atoms or a cycloalkyl group with 3 to 30 carbon atoms.

[0190] The alkyl group mentioned above can be, for example, a fluoroalkyl group (or a perfluoroalkyl group).

[0191] The aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group with 6 to 14 carbon atoms, such as phenyl, tolyl and naphthyl.

[0192] The aforementioned alkyl, cycloalkyl, and aryl groups may have substituents. There are no particular limitations on the substituents; specifically, examples include halogen atoms such as nitro, fluorine, and chlorine atoms, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably 1 to 15 carbon atoms), alkyl (preferably 1 to 10 carbon atoms), cycloalkyl (preferably 3 to 15 carbon atoms), aryl (preferably 6 to 14 carbon atoms), alkoxycarbonyl (preferably 2 to 7 carbon atoms), acyl (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy (preferably 2 to 7 carbon atoms), alkylthio (preferably 1 to 15 carbon atoms), alkylsulfonyl (preferably 1 to 15 carbon atoms), alkyliminosulfonyl (preferably 1 to 15 carbon atoms), and aryloxysulfonyl (preferably 6 to 20 carbon atoms).

[0193] The aralkyl group in the aralkyl carboxylic acid anion is preferably an aralkyl group with 7 to 14 carbon atoms, such as benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl.

[0194] Examples of sulfonyl imide anions include saccharin anion.

[0195] The alkyl group in the bis(alkylsulfonyl)imide anion and the tri(alkylsulfonyl)methyl anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups.

[0196] Preferably, it is a fluorine atom or an alkyl group substituted with a fluorine atom.

[0197] Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion can bond with each other to form a ring structure. As a result, the acid strength increases.

[0198] Other non-nucleophilic anions include, for example, phosphorus fluoride (e.g., PF6). - ), boron fluoride (e.g., BF4) - ) and antimony fluoride (e.g., SbF6) - ).

[0199] As a non-nucleophilic anion, it is preferably an aliphatic sulfonic acid anion in which at least the d-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion in which the fluorine atom or a group having a fluorine atom is substituted, a bis(alkylsulfonyl)imide anion in which the alkyl group is substituted with a fluorine atom, or a tri(alkylsulfonyl)methylation anion in which the alkyl group is substituted with a fluorine atom. More preferably, it is a perfluoroaliphatic sulfonic acid anion (preferably with 4 to 8 carbon atoms) or a benzenesulfonic acid anion having a fluorine atom, and even more preferably, it is a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, a pentafluorobenzenesulfonic acid anion, or a 3,5-bis(trifluoromethyl)benzenesulfonic acid anion.

[0200] As a non-nucleophilic anion, anion represented by the following formula (AN1) is also preferred.

[0201] [Chemical Formula 8]

[0202]

[0203] In the general formula (AN1),

[0204] o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0205] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. Furthermore, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred.

[0206] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, it is even more preferred that Xf in both cases is a fluorine atom.

[0207] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R4 and R5 are present, R4 and R5 can be the same or different.

[0208] The alkyl groups represented by R4 and R5 may have substituents, and the number of carbon atoms is preferably 1 to 4. R4 and R5 are preferably hydrogen atoms.

[0209] Specific examples and preferred embodiments of alkyl groups substituted with at least one fluorine atom are the same as those of Xf in general formula (AN1).

[0210] L represents a binary linker. When multiple Ls exist, they can be the same or different.

[0211] Examples of divalent linkers include -O-CO-O-, -COO-, -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), alkenyl groups (preferably with 2 to 6 carbon atoms), and divalent linkers formed by combining multiple of these. Preferably, the alkylene compounds are -O-CO-O-, -CO0-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -O-CO-O-alkylene-, -alkylene-O-CO-O-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, or -NHCO-alkylene-, and more preferably -O-CO-O-, -O-CO-O-alkylene-, -alkylene-O-CO-O-, -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene-, or -OCO-alkylene-.

[0212] W represents an organic group containing a cyclic structure. Preferably, it is a cyclic organic group.

[0213] Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups.

[0214] The alicyclic group can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. Among these, alicyclic groups with a large volume structure having 7 or more carbon atoms, such as norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl, are preferred.

[0215] The aryl group can be monocyclic or polycyclic. Examples of such aryl groups include phenyl, naphthyl, phenanthryl, and anthracene.

[0216] The heterocyclic group can be monocyclic or polycyclic. Polycyclic heterocyclic groups can better suppress acid diffusion. Furthermore, the heterocyclic group can be aromatic or non-aromatic. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocycles include tetrahydropyran rings, lactone rings, sulfonyl lactone rings, and decahydroisoquinoline rings. Furan rings, thiophene rings, pyridine rings, or decahydroisoquinoline rings are particularly preferred as heterocyclic groups.

[0217] The aforementioned cyclic organic groups may have substituents. Examples of such substituents include alkyl groups (which may be linear or branched, preferably with 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably with 3 to 20 carbon atoms), aryl groups (preferably with 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, carbamate groups, urea groups, thioether groups, sulfonamide groups, and sulfonate groups. Furthermore, the carbon atom constituting the cyclic organic group (the carbon atom that contributes to ring formation) may be a carbonyl carbon.

[0218] SO3 is preferred as the anion represented by the general formula (AN1). - -CF2-CH2-OCO-(L)q'-W、SO3 - -CF2-CHF-CH2-OCO-(L)q'-W、SO3 - -CF2-COO-(L)q'-W、SO3 - -CF2-CF2-CH2-CH2-(L)qW or SO3 - -CF2-CH(CF3)-OCO-(L)q'-W. Here, L, q, and W are the same as in general formula (AN1). q' represents an integer from 0 to 10.

[0219] As a non-nucleophilic anion, anion represented by the following formula (AN2) is also preferred.

[0220] [Chemical Formula 9]

[0221]

[0222] In general formula (AN2),

[0223] X B1 and X B2 Each can be represented independently as either a hydrogen atom or a monovalent organic group without a fluorine atom. X B1 and X B2 Hydrogen atoms are preferred.

[0224] X B3 and X B4 Each can independently represent a hydrogen atom or a monovalent organic group. X is preferred. B3 and X B4 At least one of them is a fluorine atom or a monovalent organic group having a fluorine atom, more preferably X B3 and X B4 Both are fluorine atoms or monovalent organic groups having fluorine atoms. X is further preferred. B3 and X B4 Both of these are alkyl groups that have been replaced by fluorine atoms.

[0225] L, q, and W are the same as in general formula (AN1).

[0226] As a non-nucleophilic anion, the anion represented by the following formula (AN3) is preferred.

[0227] [Chemical Formula 10]

[0228]

[0229] In general formula (AN3), Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Xb independently represents a hydrogen atom or an organic group without a fluorine atom. The definitions and preferred methods of o, p, q, R4, R5, L and W are the same as in general formula (AN1).

[0230] As a non-nucleophilic anion, anion represented by the following formula (AN4) is also preferred.

[0231] [Chemical Formula 11]

[0232]

[0233] In general formula (AN4), R 1 and R 2 Each can be used independently to represent a substituent or a hydrogen atom that is not an electron-withdrawing group.

[0234] Examples of substituents that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups.

[0235] Furthermore, as a substituent that is not an electron-withdrawing group, it is preferably independently -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0236] Examples of monovalent hydrocarbon groups represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl, propynyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornyl; aryl groups such as phenyl, tolyl, xylyl, mesitylelel, naphthyl, methylnaphthyl, anthracenel, and methylanthrayl; and aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthracenemethyl.

[0237] Among them, R 1 R2 is preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom, respectively.

[0238] In general formula (AN4), L represents a divalent linker consisting of a combination of one or more linking groups S and one or more alkylene groups that may have substituents, or a divalent linker consisting of one or more linking groups S.

[0239] The linker S is selected from * A -O-CO-O-* B 、* A -CO-* B 、* A -CO-O-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B and* A -SO2-* B The groups in.

[0240] Wherein, when L is a form of "a divalent linker composed of a combination of one or more linking groups S and one or more alkylene groups that may have substituents" or "a divalent linker composed of a combination of one or more linking groups S and one or more alkylene groups that do not have substituents", the linking group S is preferably selected from * A -O-CO-O-* B 、* A -CO-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B and* A -SO2-* B The linking group. In other words, when the alkylene groups in "a divalent linking group consisting of a combination of one or more linking groups S and one or more alkylene groups that may have substituents" are all unsubstituted alkylene groups, the linking group S is preferably selected from * A -O-CO-O-* B 、* A -CO-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B and* A -SO2-* B The groups in.

[0241] * AR in general formula (AN4) 3 Side bonding position, * B The -SO3 in the general formula (AN4) - The bonding position on the side.

[0242] In a divalent linker consisting of one or more linking groups S and one or more alkylene groups that may have substituents, there may be only one linking group S or there may be two or more alkylene groups that may have substituents. When there are multiple linking groups S, the multiple linking groups S may be the same or different. When there are multiple alkylene groups, the multiple alkylene groups may be the same or different.

[0243] Furthermore, the linker bases S can be continuously bonded to each other. Preferably, they are selected from * A -CO-* B 、* A -O-CO-* B and* A -O-* B The groups in the group are continuously bonded without forming "* A -O-CO-O-* B Furthermore, it is preferred to select from * A -CO-* B and* A -O-* B The groups in the group are continuously bonded and none of them form "*". A -O-CO-* B "and"* A -CO-O-* B ".

[0244] In a divalent linkage consisting of one or more linkage bases S, there can be only one linkage base S, or there can be two or more linkage bases S. When there are multiple linkage bases S, the linkage bases S can be the same or different.

[0245] At this time, it is also preferable to select from * A -CO-* B 、* A -O-CO-* B and* A -O-* B The groups in the group are continuously bonded without forming "* A -O-CO-O-* B Furthermore, it is preferred to select from * A -CO-* B and* A -O-* BThe groups in the group are continuously bonded and none of them form "*". A -O-CO-* B "and"* A -CO-O-* B ".

[0246] However, in any case, in L, relative to -SO3 - The atoms at the β position are not carbon atoms with fluorine atoms as substituents.

[0247] In addition, when the atom at the β position is a carbon atom, it is permissible for the carbon atom to be directly substituted with a fluorine atom, and the carbon atom may contain a substituent having a fluorine atom (e.g., fluoroalkyl groups such as trifluoromethyl).

[0248] Furthermore, in other words, the atom at the β position mentioned above refers to the atom corresponding to -C(R) in the general formula (AN4). 1 (R) 2 )- Atoms in L that are directly bonded.

[0249] In this case, L preferably has only one connecting base S.

[0250] That is, L preferably represents a divalent linker consisting of a combination of one linker S and one or more alkylene groups that may have substituents, or a divalent linker consisting of one linker S.

[0251] L is preferably a group represented by the following formula (AN4-2).

[0252] * a -(CR 2a 2) x -Q-(CR 2b 2) Y -* b (AN4-2)

[0253] In general formula (AN4-2), * a R in general formula (AN4) 3 The bonding positions.

[0254] * b This represents -C(R) in the general formula (AN4). 1 (R) 2 The bonding position of )-.

[0255] X and Y each independently represent integers from 0 to 10, preferably integers from 0 to 3.

[0256] R 2a and R 2b Each can be used to represent a hydrogen atom or a substituent independently.

[0257] When R 2a and R 2b When there are multiple R values, there are multiple R values. 2a and R 2b They can be the same or different.

[0258] When Y is 1 or more, it corresponds to -C(R) in the general formula (AN4). 1 (R) 2 )- Directly bonded CR 2b R in 2 2b These are atoms other than fluorine atoms.

[0259] Q represents * A -O-CO-O-* B 、* A -CO-* B 、* A -CO-O-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B or* A -SO2-* B .

[0260] Where X+Y in general formula (AN4-2) is 1 or more and R in general formula (AN4-2) 2a and R 2b When all atoms are hydrogen atoms, Q represents * A -O-CO-O-* B 、* A -CO-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B or* A -SO2-* B .

[0261] * A R in general formula (AN4) 3 Side bonding position, * B The -SO3 in the general formula (AN4) - The bonding position on the side.

[0262] In general formula (AN4), R 3 It represents an organic group.

[0263] There are no restrictions on the presence of one or more carbon atoms in the aforementioned organic groups. They can be straight-chain groups (e.g., straight-chain alkyl groups), branched-chain groups (e.g., branched alkyl groups such as tert-butyl), or cyclic structures. The aforementioned organic groups may or may not have substituents. The aforementioned organic groups may or may not have heteroatoms (oxygen atoms, sulfur atoms, and / or nitrogen atoms, etc.).

[0264] Among them, R 3 Preferably, the organic group has a cyclic structure. The cyclic structure can be monocyclic, polycyclic, or have substituents. The ring in the organic group containing the cyclic structure is preferably directly bonded to L in the general formula (AN4).

[0265] The aforementioned organic groups with cyclic structures may or may not have heteroatoms (oxygen, sulfur, and / or nitrogen atoms, etc.). A heteroatom may be replaced by one or more carbon atoms forming a cyclic structure.

[0266] The aforementioned organic groups with cyclic structures are preferably cyclic hydrocarbon groups, lactone cyclic groups, or sulfonyl lactone cyclic groups. Among them, the aforementioned organic groups with cyclic structures are preferably cyclic hydrocarbon groups.

[0267] The hydrocarbon group in the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may also have substituents.

[0268] The aforementioned cycloalkyl group can be monocyclic (such as cyclohexyl) or polycyclic (such as adamantyl), and preferably has 5 to 12 carbon atoms.

[0269] As the aforementioned lactone group and sulfonolactone group, for example, it is preferred to be a group formed by removing one hydrogen atom from the ring member atom constituting the lactone structure or sulfonolactone structure in any one of the structures represented by the general formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) described below.

[0270] As a non-nucleophilic anion, it can be a benzenesulfonic acid anion, preferably a benzenesulfonic acid anion substituted with branched alkyl or cycloalkyl groups.

[0271] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN5) is also preferred.

[0272] [Chemical Formula 12]

[0273]

[0274] In general formula (AN5),

[0275] Ar represents aryl (phenyl, etc.), and may also have substituents other than sulfonic acid anions and -(DB) groups. Examples of substituents that may be present include fluorine atoms and hydroxyl groups.

[0276] n represents an integer greater than or equal to 0. Preferably, n is an integer from 1 to 4, more preferably an integer from 2 to 3, and even more preferably 3.

[0277] D represents a single bond or a divalent linker. Examples of divalent linkers include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate groups, ester groups, and groups formed by combinations of two or more of these.

[0278] B represents a hydrocarbon group.

[0279] B is preferably an aliphatic hydrocarbon structure, more preferably isopropyl, cyclohexyl, or an aryl group that may have substituents (such as tricyclohexylphenyl).

[0280] Disulfonamide anion is preferred as a non-nucleophilic anion.

[0281] Examples of disulfonamide anions include those derived from N... - (SO2-R q )2 represents anion.

[0282] R q This indicates an alkyl group that may have substituents, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. (2 R's) q They can bond together to form a ring. 2 Rs q The groups formed by bonding together are preferably alkylene groups that can have substituents, more preferably fluoroalkylene groups, and even more preferably perfluoroalkylene groups. The number of carbon atoms in the aforementioned alkylene groups is preferably 2 to 4.

[0283] Furthermore, as the aforementioned anions, anions represented by the following formulas (d1-1) to (d1-3) can also be cited.

[0284] As the above-mentioned anions, specific compounds having anions represented by the following formulas (d1-1) to (d1-3) can also function as acid diffusion control agents as described later.

[0285] [Chemical Formula 13]

[0286]

[0287] In general formula (d1-1), R 51 This indicates a hydrocarbon group (e.g., aryl, such as phenyl) that may have substituents (e.g., hydroxyl).

[0288] In general formula (d1-2), Z 2cThis indicates a hydrocarbon group with 1 to 30 carbon atoms that can have substituents (wherein the fluorine atom is not replaced by the carbon atom adjacent to S).

[0289] Z 2c The aforementioned hydrocarbon group can be linear or branched, and can have a cyclic structure. Furthermore, the carbon atom in the aforementioned hydrocarbon group (preferably, a carbon atom that is a ring member when the aforementioned hydrocarbon group has a cyclic structure) can be a carbonyl carbon (-CO-). Examples of such hydrocarbon groups include norbornyl groups, which can have substituents. The carbon atom forming the aforementioned norbornyl group can be a carbonyl carbon.

[0290] Furthermore, in the general formula (d1-2), "Z" 2c -SO3 - "Preferred anions are different from those represented by the formulas (AN1) to (AN5) above. For example, Z..." 2c Preferably, it contains groups other than aryl groups. And, for example, Z 2c In, relative to -SO3 - The atoms at the α and β positions are preferably atoms other than carbon atoms that have fluorine atoms as substituents. For example, Z 2c In, relative to -SO3 - The atom at the d-position and / or the atom at the β-position are preferably ring-member atoms in the cyclic group.

[0291] In general formula (d1-3), R 52 Y represents an organic group (preferably a hydrocarbon group with a fluorine atom). 3 Rf indicates a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf indicates a hydrocarbon group.

[0292] Examples of anions are shown below.

[0293] [Chemical Formula 14]

[0294]

[0295] [Chemical Formula 15]

[0296]

[0297] As described above, a particular compound has one or more cations represented by general formula (1).

[0298] There is no particular limitation on the number of organic anions in a particular compound. When the number of cations represented by general formula (1) in a particular compound is 1, the number of organic anions is preferably 1.

[0299] (Compounds represented by general formula (2))

[0300] From the viewpoint of achieving better results with respect to the present invention, compounds represented by general formula (2) are preferred as specific compounds. The compound represented by general formula (2) corresponds to a salt compound having one cation represented by general formula (1) and one organic anion.

[0301] General formula (2)Z1 + Y1 -

[0302] In general formula (2), Z1 + This refers to the cation represented by the general formula (1) above. The definition of the cation represented by the general formula (1) is as described above.

[0303] Y1 - This refers to organic anions with a monovalent valence. An organic anion with a monovalent valence refers to the organic anion with a monovalent valence among the aforementioned organic anions.

[0304] (Compounds represented by the general formula (S-1))

[0305] The preferred specific compound (a compound represented by general formula (2)) is a compound represented by general formula (S-1).

[0306] [Chemical Formula 16]

[0307]

[0308] In general formula (S-1), Y1 - This refers to organic anions with a monovalent valence. An organic anion with a monovalent valence refers to the organic anion with a monovalent valence among the aforementioned organic anions.

[0309] R S1 ~R S3 Each group can be represented independently by the general formula (T-1). Wherein, R S1 ~R S3 Preferably, the same group is represented.

[0310] In general formula (T-1), * represents the bonding position.

[0311] General formula (T-1)*-SX d2

[0312] In general formula (T-1), X d2 This refers to the group represented by the above general formula (1-1) or the detached group that is removed by the action of an acid.

[0313] By X d2 The definitions of the groups represented are as described above.

[0314] R b1 ~R b3Each substituent is represented independently, excluding the group represented by the general formula (T-1). Examples of such substituents include linear or branched alkyl groups that may have substituents, cycloalkyl groups that may have substituents, and aryl groups that may have substituents.

[0315] There is no particular limitation on the number of carbon atoms of the above-mentioned alkyl and cycloalkyl groups, but the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0316] As the above-mentioned substituent, it is preferred to be a straight-chain or branched alkyl group that may have substituents, and more preferably a straight-chain or branched alkyl group that may have heteroatoms.

[0317] Additionally, R b1 and R b2 R b2 and R b3 R b1 and R b3 They can bond together to form single bonds, or they can form divalent linkers (e.g., -O-).

[0318] a1 represents an integer from 1 to 5, a2 represents an integer from 0 to 5, and a3 represents an integer from 0 to 5.

[0319] b1 represents an integer from 0 to 4, b2 represents an integer from 0 to 5, and b3 represents an integer from 0 to 5.

[0320] The sum of a1 and b1 represents an integer from 1 to 5, the sum of a2 and b2 represents an integer from 0 to 5, and the sum of a3 and b3 represents an integer from 0 to 5.

[0321] Wherein, a1 to a3 preferably represent integers 1 to 3 independently, and more preferably represent integers 1 to 2 independently.

[0322] Furthermore, the sum of a1, a2, and a3 is preferably an integer from 1 to 5, and more preferably an integer from 1 to 3.

[0323] b1 to b3 preferably represent integers from 0 to 3 independently, and more preferably represent integers from 0 to 2 independently.

[0324] Furthermore, the sum of b1, b2, and b3 is preferably an integer from 0 to 5, and more preferably an integer from 0 to 3.

[0325] As a specific compound, examples include compounds having two or more cation sites and the same number of anionic sites as the aforementioned cation sites, wherein at least one of the aforementioned cation sites is a specific cation (hereinafter also simply referred to as "compound W").

[0326] A cation site is a structural site containing a positively charged atom or group of atoms. As described above, in compound W, at least one of the two or more cation sites is a specific cation. From the viewpoint of further enhancing the effects of the present invention, it is preferable that all two or more cation sites contained in compound W are specific cations.

[0327] Furthermore, in compound W, at least one of the two or more cation sites needs to be a specific cation, and it may include organic cations other than the specific cation. Examples of organic cations other than the specific cation include sulfonium cations and iodonium ions.

[0328] An anionic site is a structural site containing a negatively charged atom or group of atoms. For example, anionic functional groups that may exist in compound W can be designated as anionic sites.

[0329] Compound W preferably has an organic anion having the same number of anionic functional groups as the cation sites of compound W.

[0330] As described above, compound W has two or more (preferably two to three) cation sites and the same number of anionic sites as the cation sites.

[0331] That is, compound W has two or more (preferably two to three) anionic sites (preferably anionic functional groups). Multiple anionic functional groups can be connected by single bonds or linkers.

[0332] Examples of anionic functional groups mentioned above include -SO3. - and as part of -SO3 - The group, -COO - and as part of -COO - The group, as part of which has -N - - groups, and as part of having a carboanion (-C - <) group.

[0333] As a specific example of anionic functional groups, groups represented by general formulas (B-1) to (B-13) described later are preferred.

[0334] [Chemical Formula 17]

[0335]

[0336] In general formulas (B-1) to (B-13), * indicates the bonding position.

[0337] In addition, the * in general formula (B-12) is preferably a bonding position relative to a group that is not either -CO- or -SO2-.

[0338] In general formulas (B-1) to (B-5) and (B-12), R X1 It represents an organic group.

[0339] As R X1 Preferably, it is a linear, branched, or cyclic alkyl group, or an aryl group that may have substituents.

[0340] The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10.

[0341] The alkyl group described above may have substituents. Fluorine atoms or cyano groups are preferred as substituents. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0342] Furthermore, in the aforementioned alkyl groups, the carbon atom can be replaced by a carbonyl group.

[0343] The aryl group is preferably phenyl or naphthyl, and more preferably phenyl.

[0344] The aryl group described above may have substituents. Preferred substituents are fluorine atoms, perfluoroalkyl groups (preferably with 1 to 10 carbon atoms, more preferably with 1 to 6 carbon atoms), or cyano groups.

[0345] Additionally, in general formula (B-5), R X1 The atom that is directly bonded to N is preferably not either the carbon atom in -CO- or the sulfur atom in -SO2-.

[0346] Additionally, R in general formula (B-3) X1 Preferably, it does not contain fluorine atoms.

[0347] In general formulas (B-7) and (B-11), R X2 It indicates a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group.

[0348] As a result of R X2 The fluorine atom and substituents other than perfluoroalkyl are represented, preferably alkyl groups other than perfluoroalkyl (which can be any of straight-chain, branched, or cyclic).

[0349] The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10.

[0350] The alkyl group described above preferably does not have a fluorine atom. That is, when the alkyl group has a substituent, it is preferably a substituent other than a fluorine atom.

[0351] In general formula (B-8), R XF1This indicates a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. Multiple R groups are included. XF1 At least one of them represents a fluorine atom or a perfluoroalkyl group.

[0352] By R XF1 The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

[0353] In general formula (B-10), R XF2 It indicates a fluorine atom or a perfluoroalkyl group.

[0354] By R XF2 The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

[0355] In general formula (B-9), n represents an integer from 0 to 4.

[0356] As a result of A 11 - and A 12 - There are no particular restrictions on the combination of anionic functional groups represented; for example, when A... 11 - When it is a group represented by the general formula (B-8) or (B-10), it is treated as a group composed of A. 12 - Examples of anionic functional groups can be those represented by general formulas (B-1) to (B-7), (B-9), or (B-11) to (B-13), when A 11 - When it is a group represented by the general formula (B-7), it is treated as a group composed of A. 12 - The anionic functional group represented can be exemplified by groups represented by the general formula (B-6), when A 11 - When the group is represented by the general formula (B-9), it is represented by A. 12 - The anionic functional group represented can be exemplified by groups represented by the general formula (B-6), when A 11 - When the group is represented by the general formula (B-1), it is represented by A. 12 - The anionic functional groups represented can be exemplified by groups represented by the general formula (B-3).

[0357] Among them, compound W preferably has an anionic site A. B - (Anionic functional group A) B - ) as the anion site.

[0358] Anion site A B - (Anionic functional group A) B - ) is a group represented by any one of the general formulas (BX-1) to (BX-4).

[0359] [Chemical Formula 18]

[0360]

[0361] In the general formulas (BX-1) to (BX-4), * indicates the bonding position.

[0362] In general formulas (BX-1) to (BX-4), R B It represents an organic group.

[0363] As R B Examples of organic groups in formulas (B-1) to (B-5) and (B-12) can also be cited as R. X1 Examples of organic groups.

[0364] Furthermore, compound W preferably has the anion site A mentioned above. B - (Anionic functional group A) B - In addition to ) it also has an anion site A A - (Anionic functional group A) A - ) as the anion site.

[0365] Anion site A A - (Anionic functional group A) A - ) is a group represented by any one of the general formulas (AX-1) to (AX-2).

[0366] [Chemical Formula 19]

[0367]

[0368] In the general formulas (AX-1) to (AX-2), * indicates the bonding position.

[0369] In the general formula (AX-2), R A It represents an organic group.

[0370] R A Alkyl groups are preferred.

[0371] The alkyl groups mentioned above can be straight-chain or branched.

[0372] The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5.

[0373] The alkyl group may preferably have fluorine atoms as a substituent.

[0374] The alkyl group described above, which has a fluorine atom as a substituent, may or may not be a perfluoroalkyl group.

[0375] Compound W, as an anionic site, in addition to having the aforementioned anionic site A, B - (Anionic functional group A) B - ) and the above-mentioned anion site A A - (Anionic functional group A) A - In addition to the above, it may or may not have further anionic sites (preferably further anionic functional groups).

[0376] As compound W, it is preferred to be a compound represented by general formula (3).

[0377] [Chemical Formula 20]

[0378]

[0379] In general formula (3), Z2 + Z2 represents a cation. + At least one of them represents a cation represented by general formula (1).

[0380] The definition of a cation represented by general formula (1) is as described above. There are no particular limitations on cations other than those represented by general formula (1), and well-known examples include sulfonium cations and iodonium cations.

[0381] Multiple Z + At least one Z + Any specific cation is acceptable, but from the viewpoint of achieving better results in this invention, two or more Z cations are preferred. + For a specific cation, more preferably all Z + It is a specific cation.

[0382] Y2 - This indicates an anionic functional group. The definition of an anionic functional group is as described above. Multiple Y2 groups exist. - They can be the same or different.

[0383] There are multiple Y2 -For example, it may have at least "a group represented by general formula (B-8) or (B-10), a group represented by general formula (B-1) to (B-7), (B-9), or (B-11) to (B-13)," or it may have at least "a group represented by general formula (B-7) and a group represented by general formula (B-6)," or it may have at least "a group represented by any one of general formula (BX-1) to (BX-4) and a group represented by any one of general formula (AX-1) to (AX-2)."

[0384] q represents an integer greater than 2. From the viewpoint of achieving better results in this invention, q is preferably an integer from 2 to 5, and more preferably an integer from 2 to 3.

[0385] L represents the q-valence linker.

[0386] For example, when q is 2, L represents a 2-valent linker.

[0387] Examples of divalent linkers include -COO-, -CONH-, -CO-, -O-, alkylene groups (preferably with 1 to 6 carbon atoms, which can be straight-chain or branched), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), and divalent linkers formed by combining multiple of these.

[0388] One or more methylene groups of the cycloalkane ring constituting the above-mentioned cycloalkyl group may be replaced by carbonyl carbon and / or heteroatoms (oxygen atoms, etc.).

[0389] These divalent linkers are also preferably further selected from -S-, -SO-, -SO2-, and -NR. N -(R N (A group consisting of a hydrogen atom or a substituent).

[0390] As a linker with a valence of 3 or higher, examples include linking single bonds and / or the groups that are desirable for a divalent linker with -CR. q A group consisting of <, -N<, >C<, a hydrocarbon cyclic group with a valence of 3 or higher, and / or a heterocyclic group with a valence of 3 or higher. R q It represents a hydrogen atom or a substituent.

[0391] As a specific compound, compounds (IA) to (III-A) described later are also preferred.

[0392] (Compound (1-A))

[0393] The following describes compound (IA).

[0394] Compound (IA): is a compound having one of the following structural sites X and one of the following structural sites Y, respectively, and which, upon irradiation with photochemical rays or radiation, produces an acid comprising the first acidic site derived from structural site X and the second acidic site derived from structural site Y.

[0395] Structural site X: composed of anion site A1 - and cation site M1 + It is composed of, and through irradiation by photochemical rays or radiation, forms the structural site of the first acidic region represented by HA1.

[0396] Structural region Y: composed of anion site A2 - and cation site M2 + The structure is composed of a second acidic region, represented by HA2, which has a different structure from the first acidic region formed in the aforementioned structural region X, and is formed by irradiation with photochemical rays or radiation.

[0397] Among them, the cation site M1 + and cation site M2 + At least one of them is a specific cation.

[0398] Furthermore, compound (IA) satisfies the following condition I.

[0399] Condition I: In the above compound (IA), the above-mentioned cation site M1 in the above-mentioned structural site X is... + and the aforementioned cation site M2 in the aforementioned structural site Y. + Replace with H + The resulting compound PI has an acid dissociation constant a1, derived from the cation M1 in the above-mentioned structural site X. + Replace with H + The acidic site represented by HA1 and the acid dissociation constant a2 are derived from the cation site M2 in the above structural site Y. + Replace with H + The acidic site represented by HA2 is formed, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0400] Furthermore, the acid dissociation constants a1 and a2 are obtained using the method described above. More specifically regarding the acid dissociation constants a1 and a2 of compound PI, when determining the acid dissociation constants of compound PI, compound PI (compound PI is equivalent to "a compound having HA1 and HA2") becomes "a compound having A1..." - The pKa of compounds containing HA2 is the acid dissociation constant a1. The above-mentioned compounds containing A1... - Compounds containing HA2" become "compounds with A1- and A2 - The pKa of the compound is the acid dissociation constant a2.

[0401] Furthermore, the aforementioned compound PI is equivalent to an acid produced by irradiating compound (IA) with photochemical rays or radiation.

[0402] From the viewpoint of achieving better results with the present invention, in the above-described compound PI, the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 2.0 or more, more preferably 3.0 or more. Furthermore, there is no particular limitation on the upper limit of the difference between the acid dissociation constant a1 and the acid dissociation constant a2, but it is preferably 15.0 or less.

[0403] Furthermore, from the viewpoint of achieving better results with the present invention, in the above-described compound PI, the acid dissociation constant a2 is, for example, 6.5 or less. From the viewpoint of achieving better stability of the cationic site of compound (IA) in the resist composition, in the above-described compound PI, it is preferably 2.0 or less, more preferably 1.0 or less. In addition, as a lower limit value for the acid dissociation constant a2, it is preferably -5.0 or more, more preferably -3.5 or more, and even more preferably -2.0 or more.

[0404] Furthermore, from the viewpoint of achieving better results with the present invention, in the above-described compound PI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0.5 or less, and even more preferably -0.1 or less. Additionally, as a lower limit value for the acid dissociation constant a1, it is preferably -15.0 or more.

[0405] There are no particular limitations on the term (IA), and for example, compounds represented by the following general formula (Ia) can be cited.

[0406] M 11 + A 11 - -L1-A 12 - M 12 + (Ia)

[0407] In general formula (Ia), "M 11 + A 11 - "and "A 12 - M 12 + These correspond to structural sites X and Y, respectively. Compound (Ia) produces HA by irradiation with photochemical rays or radiation. 11 -L1-A 21 H represents an acid. That is, "M"11 + A 11 - "Formed by HA" 11 The first acidic site, "A" 12 - M 12 + "Formed by HA with a structure different from the first acidic site mentioned above" 12 The second acidic site is indicated.

[0408] In general formula (Ia), M 11 + and M 12 + Each can be used to represent a cation (a specific cation or an organic cation other than a specific cation).

[0409] M 11 + and M 12 + At least one (preferably both) of them is a specific cation.

[0410] A 11 - and A 12 - Each of these independently represents anionic functional groups. Among them, A... 12 - Indicates the relationship with A 11 - The different structures of the anionic functional groups are represented.

[0411] L1 represents a bivalent linker.

[0412] In the above general formula (Ia), M will be... 11 + and M 12 + The specific cation substitution is H. + The compound formed is PIa(HA) 11 -L1-A 12 In H), it originates from A 12 The acid dissociation constant a2 of the acidic site represented by H is greater than that derived from HA. 11 The acid dissociation constant a1 represents the acidic region. Furthermore, preferred values ​​for acid dissociation constants a1 and a2 are as described above.

[0413] In general formula (Ia), M 11 + and M 12 + Each can be used to represent a cation (a specific cation or an organic cation other than a specific cation).

[0414] M 11 + and M 12 + At least one (preferably both) of them is a specific cation.

[0415] The above applies to specific cations.

[0416] For organic cations other than specific cations, the above applies.

[0417] In general formula (Ia), A 11 - and A 12 - Each of these independently represents anionic functional groups. Among them, A... 12 - Indicates the relationship with A 11 - The different structures of the anionic functional groups are represented.

[0418] For anionic functional groups, as described above.

[0419] A 11 - and A 12 - The anionic functional groups are preferably groups represented independently by the above general formulas (B-1) to (B-13).

[0420] As a result of A 11 - and A 12 - There are no particular restrictions on the combination of anionic functional groups represented; for example, when A... 11 - When it is a group represented by the general formula (B-8) or (B-10), it is treated as a group composed of A. 12 - Examples of anionic functional groups can be those represented by general formulas (B-1) to (B-7), (B-9), or (B-11) to (B-13), when A 11 - When it is a group represented by the general formula (B-7), it is treated as a group composed of A. 12 - The anionic functional groups represented can be exemplified by groups represented by the general formula (B-6).

[0421] In general formula (Ia), the divalent linker represented by L1 is not particularly restricted; examples include -CO- and -NR-. L1-, -CO-, -O-, alkylene groups (preferably with 1 to 6 carbon atoms; can be straight-chain or branched), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic hydrocarbon cyclic groups (preferably 6 to 10-membered rings, and even more preferably 6-membered rings), and divalent linking groups formed by combining multiple of these. The above R L1 Examples include hydrogen atoms or monovalent organic groups. There are no particular limitations on the monovalent organic group, but alkyl groups are preferred (preferably with 1 to 6 carbon atoms).

[0422] These divalent linkers may also include groups selected from -S-, -SO-, and -SO2-.

[0423] Furthermore, the aforementioned alkylene group, cycloalkylene group, alkenyl group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon cyclic group can be substituted with substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0424] Among them, the compound (IA) is preferably a compound represented by the general formula (Ib).

[0425] M1 + A - -LB - M2 + (Ib)

[0426] In general formula (Ib), M1 + and M c + Each can be used to represent a cation (a specific cation or an organic cation other than a specific cation).

[0427] M1 + and M2 + At least one (preferably both) of them represents a specific cation.

[0428] The above applies to specific cations.

[0429] The same applies to organic cations other than specific cations.

[0430] In the general formula (Ib), L represents a divalent organic group.

[0431] Examples of divalent organic groups include -COO-, -CONH-, -CO-, -O-, alkylene groups (preferably with 1 to 6 carbon atoms, which can be straight-chain or branched), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple of these.

[0432] One or more methylene groups of the cycloalkane ring constituting the above-mentioned cycloalkyl group may be replaced by carbonyl carbon and / or heteroatoms (oxygen atoms, etc.).

[0433] These divalent linkers also preferably have groups selected from -S-, -SO- and -SO2-.

[0434] Wherein, L is preferably a group represented by the following general formula (L).

[0435] *A-LA-LB-LC-LD-LE-*B (L)

[0436] In general formula (L), *A represents the bonding position with A in general formula (Ib).

[0437] In general formula (L), *B represents the bond position with B in general formula (Ib).

[0438] In the general formula (L), LA represents -(C(R) LA1 (R) LA2 )) XA -

[0439] The above XA represents an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 3.

[0440] R LA1 and R LA2 Each can be used to represent a hydrogen atom or a substituent independently.

[0441] As R LA1 and R LA2 The substituents are each preferably fluorine atoms or fluoroalkyl groups, more preferably fluorine atoms or perfluoroalkyl groups, and even more preferably fluorine atoms or perfluoromethyl groups.

[0442] When XA is 2 or more, there are XA R's. LA1 They can be the same or different.

[0443] When XA is 2 or more, there are XA R's. LA2 They can be the same or different.

[0444] -(C(R LA1 (R) LA2Preferred values ​​are -CH2-, -CHF-, -CH(CF3)-, or -CF2-.

[0445] Among them, in the general formula (Ib) and A - Directly bonded -(C(R) LA1 (R) LA2 Preferred values ​​are -CH2-, -CHF-, -CH(CF3)-, or -CF2-.

[0446] In general formula (Ib), -(C(R) directly bonded to A LA1 (R) LA2 ))- other than -(C(R LA1 (R) LA2 -The preferred options are -CH2-, -CHF-, or -CF2-, respectively.

[0447] In the general formula (L), LB represents a single bond, an ester group (-COO-) or a sulfonyl group (-SO2-).

[0448] In the general formula (L), LC represents a single bond, alkylene, cycloalkylene, or a combination thereof ("-alkylene-cycloalkyl-", etc.).

[0449] The aforementioned alkylene groups can be linear or branched.

[0450] The number of carbon atoms in the aforementioned alkylene group is preferably 1 to 5, more preferably 1 to 2, and even more preferably 1.

[0451] The number of carbon atoms in the aforementioned cycloalkyl group is preferably 3 to 15, more preferably 5 to 10.

[0452] The aforementioned cycloalkyl groups can be monocyclic or polycyclic.

[0453] Examples of the aforementioned cycloalkyl groups include norbornenediyl and adamantanediyl.

[0454] The substituents that may be present as the above-mentioned cycloalkyl group are preferably alkyl groups (which may be straight-chain or branched. Preferably, they have 1 to 5 carbon atoms).

[0455] One or more methylene groups of the cycloalkane ring constituting the above-mentioned cycloalkyl group may be replaced by carbonyl carbon and / or heteroatoms (oxygen atoms, etc.).

[0456] When LC is “-alkylene-cycloalkylene-”, the alkylene portion is preferably present on the LB side.

[0457] When LB is a single bond, LC is preferably a single bond or a cycloalkylene compound.

[0458] In the general formula (L), LD represents a single bond, an ether group (-O-), a carbonyl group (-CO-), or an ester group (-COO-).

[0459] In the general formula (L), LE represents a single bond or -(C(R) LF1 (R) LE2 )) XE -

[0460] The above -(C(R) LE1 (R) LE2 )) XE In the -, XE represents an integer greater than or equal to 1, preferably 1 to 10, and more preferably 1 to 3.

[0461] R LE1 and R LE2 Each can be used to represent a hydrogen atom or a substituent independently.

[0462] When XE is 2 or more, there are XE types of R. LE1 They can be the same or different.

[0463] When XE is 2 or more, there are XE types of R. LE2 They can be the same or different.

[0464] Among them, -(C(R) LE1 (R) LE2 - Preferably -CH2- or -CF2-.

[0465] In general formula (L), when LB, LC and LD are single bonds, it is preferred that LE is also a single bond.

[0466] In general formula (Ib), A - and B - Each can be used to represent anionic functional groups independently.

[0467] For anionic functional groups, as described above.

[0468] Among them, A - Preferably, it is a group represented by any one of the general formulas (AX-1) to (AX-2).

[0469] B - Preferably, it represents a group represented by any one of the general formulas (BX-1) to (BX-4).

[0470] A - and B - Preferably, they have different structures.

[0471] Among them, A is preferred. - For groups represented by the general formula (AX-1), and B -A group or A represented by any one of the general formulas (BX-1) to (BX-4) - For groups represented by the general formula (AX-2), and B - It is a group represented by any one of the general formulas (BX-1), (BX-3), and (BX-4).

[0472] Among them, in the compound represented by general formula (Ib), M1 + and M2 + In the compounds represented by HA-L-BH, which are respectively substituted with hydrogen atoms, the pKa of the group represented by HA is lower than that of the group represented by BH.

[0473] More specifically, when determining the acid dissociation constant of a compound represented by HA-L-BH, "HA-L-BH" is changed to "A". - The pKa of "-L-BH" is set to "the pKa of the group represented by HA". Furthermore, "A" is set to... - -L-BH" becomes "A" - -LB - The pKa of the group represented by BH is set as "the pKa of the group represented by BH".

[0474] The pKa of the group represented by HA and the pKa of the group represented by BH are obtained using either software package 1 or Gaussian16.

[0475] For example, the pKa of the group represented by HA is equivalent to the acid dissociation constant a1 mentioned above, and the preferred range is also the same.

[0476] The pKa of the group represented by BH is equivalent to the acid dissociation constant a2 mentioned above, and the preferred range is also the same.

[0477] The difference between the pKa of the group represented by HB and the pKa of the group represented by HA ("pKa of the group represented by HB" - "pKa of the group represented by HA") is equivalent to the difference between the acid dissociation constant a1 and the acid dissociation constant a2 mentioned above, and the preferred range is also the same.

[0478] Next, compound (II-A) will be described.

[0479] Compound (II-A): is a compound having two or more of the above-described structural sites X and Y, and which, upon irradiation with photochemical rays or radiation, produces an acid comprising two or more of the first acidic sites derived from the above-described structural site X and the second acidic sites derived from the above-described structural site Y.

[0480] Among them, the cation site M1 + and cation site M2 +At least one of them is a specific cation.

[0481] Furthermore, compound (II-A) satisfies condition II.

[0482] Condition II: In the above compound (II-A), the above-mentioned cation site M1 in the above-mentioned structural site X is... + and the cation site M2 in the aforementioned structural site Y. + Replace with H + The resulting compound PII has an acid dissociation constant a1, derived from the cation M1 in the above-mentioned structural site X. + Replace with H + The acidic site represented by HA1 and the acid dissociation constant a2 are derived from the cation site M2 in the above structural site Y. + Replace with H + The acidic site represented by HA2 is formed, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0483] The acid dissociation constants a1 and a2 were determined using the method described above.

[0484] Here, the acid dissociation constants a1 and a2 of compound PII will be explained in more detail. When compound (II-A) is, for example, a compound that produces an acid having two acidic sites derived from the first acidic site X and one acidic site derived from the second acidic site Y, compound PII is equivalent to "a compound having two HA1 and one HA2". When determining the acid dissociation constant of compound PII, compound PII becomes "a compound having one A1". - The pKa of compounds containing 1 HA1 and 1 HA2 is the acid dissociation constant a1, and the pKa of compounds containing 2 A1s is the acid dissociation constant a1. - A compound with one HA2 group becomes a compound with two A1 groups. - and 1 A2 - The pKa of the compound is the acid dissociation constant a2. That is, when the compound PII has multiple cation sites M1 derived from the above-mentioned structural site X, the pKa is the acid dissociation constant a2. + Replace with H + When the acid dissociation constant of the acidic site is represented by HA1, its minimum value is regarded as the acid dissociation constant a1.

[0485] Furthermore, the aforementioned compound PII is equivalent to an acid produced by irradiating compound (II-A) with photochemical rays or radiation.

[0486] In addition, compound (II-A) may have multiple of the above-mentioned structural sites Y.

[0487] From the viewpoint of achieving better results with the present invention, in the above-described compound PII, the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 2.0 or more, more preferably 3.0 or more. Furthermore, there is no particular limitation on the upper limit of the difference between the acid dissociation constant a1 and the acid dissociation constant a2, for example, it is 15.0 or less.

[0488] Furthermore, in the above-mentioned compound PII, the acid dissociation constant a2 is preferably 6.5 or less, and from the viewpoint that the stability of the cationic site of compound (II-A) in the resist composition is superior, it is more preferably 2.0 or less, and even more preferably 1.0 or less. In addition, as a lower limit value of the acid dissociation constant a2, it is preferably -2.0 or more.

[0489] Furthermore, from the viewpoint of achieving better results with the present invention, in the above-described compound PII, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0.5 or less, and even more preferably -0.1 or less. Additionally, as a lower limit value for the acid dissociation constant a1, it is preferably -15.0 or more.

[0490] There are no particular limitations on the compound (II-A), for example, compounds represented by the following general formula (IIa) can be cited.

[0491] [Chemical Formula 21]

[0492]

[0493] In general formula (IIa), "M 21 + A 21 - "and "A 22 - M 22 + "These correspond to structural sites X and Y, respectively. Compound (IIa) produces an acid represented by the following general formula (IIa-1) upon irradiation with photochemical rays or radiation. That is, "M 21 + A 21 - "Formed by HA" 21 The first acidic site, "A" 22 - M 22 + "Formed by HA with a structure different from the first acidic site mentioned above" 22 The second acidic site is indicated.

[0494] [Chemical Formula 22]

[0495]

[0496] In general formula (IIa), M 21 + and M 22 + Each can be used to represent a cation (a specific cation or an organic cation other than a specific cation).

[0497] M 21 + and M 22 + At least one (preferably both) of them represents a specific cation.

[0498] A 21 - and A 22 - Each of these independently represents anionic functional groups. Among them, A... 22 - Indicates the relationship with A 21 - The different structures of the anionic functional groups are represented.

[0499] L2 represents an organic group with a valence of (n1+n2).

[0500] n1 represents an integer greater than or equal to 2.

[0501] n2 represents an integer greater than or equal to 1.

[0502] In the above general formula (IIa), when M is... 21 + and M 22 + The cation substitution represented is H. + The resulting compound PIIa (equivalent to the compound represented by the above general formula (IIa-1)) is derived from A 22 The acid dissociation constant a2 of the acidic site represented by H is greater than that derived from HA. 21 The acid dissociation constant a1 represents the acidic region. Furthermore, preferred values ​​for acid dissociation constants a1 and a2 are as described above.

[0503] In the above general formula (IIa), M 21 + M 22 + A 21 - and A 22 - Each of the above general formulas (Ia) and M 11 + M 12 + A 11 - and A12 - The meanings are the same, and the preferred methods are also the same.

[0504] In the above general formula (IIa), n1 M 21 + Each other, n1 A 21 + Each of them represents the same group.

[0505] In the above general formula (IIa), there is no particular limitation on the organic group with a valence of (n1+n2) represented by L2; for example, groups represented by the following general formulas (A1) and (A2) can be included. Furthermore, in the following general formulas (A1) and (A2), at least two of the * radicals represent groups with the valence A. 21 - The bonding positions, * at least one of which indicates a bond with A 22 - The bonding positions.

[0506] [Chemical Formula 23]

[0507]

[0508] In the above general formulas (A1) and (A2), T 1 T represents a trivalent hydrocarbon cyclic group or a trivalent heterocyclic group. 2 It represents a carbon atom, a tetravalent hydrocarbon cyclic group, or a tetravalent heterocyclic group.

[0509] The aforementioned hydrocarbon cyclic group can be an aromatic hydrocarbon cyclic group or an aliphatic hydrocarbon cyclic group. The number of carbon atoms contained in the aforementioned hydrocarbon cyclic group is preferably 6 to 18, more preferably 6 to 14.

[0510] The aforementioned heterocyclic group can be an aromatic heterocyclic group or an aliphatic heterocyclic group. The aforementioned heterocycle is preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring.

[0511] Furthermore, in the above general formulas (A1) and (A2), L 21 and L 22 Each can be used to independently represent a single bond or a divalent linker.

[0512] As a result of L 21 and L 22 The divalent linker represented here has the same meaning as the divalent linker represented by L1 in the above general formula (Ia), and the preferred method is also the same.

[0513] n1 represents an integer greater than or equal to 2. There is no particular upper limit; for example, it can be an integer less than or equal to 6, preferably an integer less than or equal to 4, and more preferably an integer less than or equal to 3.

[0514] n² represents an integer greater than or equal to 1. There is no particular upper limit; for example, it can be an integer less than or equal to 3, but preferably less than or equal to 2.

[0515] (Compound (II1-A))

[0516] Next, compound (III-A) will be described.

[0517] Compound (III-A): is a compound having two or more of the above-described structural sites X and Z, and which, upon irradiation with photochemical rays or radiation, produces an acid comprising two or more of the above-described first acidic sites derived from structural site X and structural site Z.

[0518] Structural site Z: The nonionic organic site that can neutralize the acid.

[0519] Among them, the cation site M1 + At least one of them is a specific cation.

[0520] There are no particular limitations on the nonionicity of the acid in structural site Z, but for example, sites containing functional groups or electrons that can interact electrostatically with protons are preferred.

[0521] Functional groups that have groups or electrons capable of electrostatic interaction with protons include, for example, functional groups with macrocyclic compound structures such as cyclic polyethers, or functional groups with nitrogen atoms that have unshared electron pairs that do not contribute to π-conjugation. A nitrogen atom with unshared electron pairs that do not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure as shown in the following formula.

[0522] [Chemical Formula 24]

[0523]

[0524] Examples of partial structures that have functional groups or electrons capable of electrostatic interaction with protons include crown ether structures, azacrown ether structures, primary amine structures, secondary amine structures, tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary amine structures, secondary amine structures, and tertiary amine structures are preferred.

[0525] In the above compound (III-A), the above-mentioned cation M1 in the above-mentioned structural site X is... + Replace with H + From the viewpoint of having better effects than the present invention, the compound PIII derived from the above-described cation M1 in the above-described structural site X is superior. + Replace with H +The acid dissociation constant a1 of the acidic portion represented by HA1 is preferably 2.0 or less, more preferably 0.5 or less, and even more preferably -0.1 or less. Furthermore, as a lower limit value for the acid dissociation constant a1, it is preferably -15.0 or more.

[0526] Furthermore, when compound PIII has multiple cation sites M1 derived from the aforementioned structural site X, + Replace with H + When the acid dissociation constant of the acidic site is represented by HA1, its minimum value is regarded as the acid dissociation constant a1.

[0527] That is, when compound (III-A) is, for example, a compound that produces an acid having two acids derived from the first acidic site X and the acid from the aforementioned structural site Z, compound PIII is equivalent to "a compound having two HA1 atoms". When determining the acid dissociation constant of compound PIII, compound PIII becomes "a compound having one A1 atom". - The pKa of a compound containing one HA1 is the acid dissociation constant a1. That is, when compound PIII has multiple cation sites M1 derived from the above-mentioned structural site X, the pKa is the acid dissociation constant a1. + Replace with H + When the acid dissociation constant of the acidic site is represented by HA1, its minimum value is regarded as the acid dissociation constant a1.

[0528] Furthermore, in the above compound (III-A), the above-mentioned cation site M1 in the above-mentioned structural site X is... + Replace with H + The compound PIII refers to, for example, when compound (II1-A) is represented by compound (IIIa) described later, it is equivalent to HA. 31 -L3-N(R 2X )-L4-A 31 H.

[0529] There are no particular limitations on the compound (III-A), for example, compounds represented by the following general formula (IIIa) can be cited.

[0530] [Chemical Formula 25]

[0531]

[0532] In general formula (IIIa), "M 31 + A 31 - 'Equivalent to structural site X. Compound (IIIa) is produced by irradiation with photochemical rays or radiation from HA.' 31 -L3-N(R 2X)-L4-A 31 H represents an acid. That is, "M" 31 + A 31 - "Formed by HA" 31 The first acidic site is indicated.

[0533] In general formula (IIIa), M 31 + It indicates a specific cation.

[0534] A 31 - It represents an anionic functional group.

[0535] L3 and L4 independently represent the divalent linker bases.

[0536] R 2X This represents an organic group with a monovalent valence.

[0537] In the above general formula (IIIa), M 31 + and A 31 - Each of the above general formulas (Ia) and M 11 + and A 11 - The meanings are the same, and the preferred methods are also the same.

[0538] In the above general formula (IIIa), L3 and L4 have the same meaning as L1 in the above general formula (Ia), and the preferred methods are also the same.

[0539] In the above general formula (IIIa), there are 2 M 31 + Each other and 2 A's 31 - Each of them represents the same group.

[0540] In general formula (IIIa), as R 2X The monovalent organic group represented is not particularly limited. For example, -CH2- can be substituted by one or more combinations selected from -CO-, -NH-, -O-, -S-, -SO- and -SO2-, alkyl (preferably with 1 to 10 carbon atoms, which can be straight-chain or branched), cycloalkyl (preferably with 3 to 15 carbon atoms), or alkenyl (preferably with 2 to 6 carbon atoms).

[0541] Furthermore, the aforementioned alkylene group, cycloalkylene group, and alkenylene group can be substituted with substituents.

[0542] The molecular weight of the compounds represented by the above compounds (IA) to (III-A) is preferably 300 to 3000, more preferably 500 to 2000, and even more preferably 700 to 1500.

[0543] Specific examples of particular compounds are shown below, but the invention is not limited thereto.

[0544] [Chemical Formula 26]

[0545]

[0546] [Chemical Formula 27]

[0547]

[0548] In the compositions of the present invention, the content of a particular compound is preferably 1.0 to 70.0% by mass, more preferably 5.0 to 70.0% by mass, further preferably 10.0 to 60.0% by mass, and especially preferably 10.0 to 60.0% by mass, relative to the total solid content of the composition.

[0549] In addition, solid components refer to components in a composition other than solvents. Any component other than solvents, even liquid components, are considered solid components.

[0550] Furthermore, a particular compound can be used in one form or in combination with multiple forms.

[0551] <A resin containing repeating units with groups whose polarity increases through acid decomposition (resin (A))>

[0552] The compositions of the present invention comprise a resin (hereinafter also referred to as "acid-degradable resin" or "resin (A)") containing repeating units having groups whose polarity increases upon decomposition by the action of acid.

[0553] That is, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0554] Resin (A) contains repeating units having groups whose polarity increases through acid decomposition (hereinafter also referred to as "acid-decomposing groups").

[0555] As described above, resin (A) sometimes contains repeating units (specific repeating units) having cations (specific cations) represented by the above general formula (1), in addition to repeating units having acid-degradable groups.

[0556] The specific cation possessed by a particular repeating unit is defined as described above.

[0557] There are no particular restrictions on the structure of a specific repeating unit, but from the viewpoint of achieving better results in this invention, repeating units represented by the general formula (U) are preferred.

[0558] [Chemical Formula 28]

[0559]

[0560] In the general formula (U), R U1 This indicates a hydrogen atom or a substituent. There are no particular restrictions on the types of substituents; examples include alkyl groups and halogen atoms.

[0561] L U1 This refers to a linker group that has a single bond or is divalent. Examples of divalent linkers include -O-, -OC-, -CO-, -COO-, -OCO-, -S-, -N-, CS-, -SO-, -SO2-, hydrocarbon groups that may have substituents (e.g., alkylene, cycloalkylene, alkenyl, and aryl groups), and linkers formed by linking multiple of these groups.

[0562] Y2 - This indicates anionic functional groups. The definition of anionic functional groups is as described above.

[0563] Z2 + Indicates a specific cation. Z2 + The definition of Z2 in the above general formula (3) is the same as that in the above general formula (3). + They have the same meaning.

[0564] When resin (A) has a specific repeating unit, the content of the specific repeating unit is not particularly limited. From the viewpoint of better effect of the present invention, it is preferably 10 to 90 mol% relative to all repeating units of resin (A), more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol%.

[0565] (Repeating unit with acid-degrading groups)

[0566] An acid-degradable group is a group that decomposes to produce a polar group through the action of an acid. Preferably, the acid-degradable group has a structure protected by a release group, where the polar group is released through the action of an acid. That is, the resin (A) contains repeating units containing groups that decompose to produce polar groups through the action of an acid. The resin containing these repeating units becomes more polar through the action of an acid, thereby increasing its solubility in alkaline developing solutions and decreasing its solubility in organic solvents.

[0567] As a polar group, an alkaline-soluble group is preferred. Examples include carboxyl, phenolic hydroxyl, fluorinated alcohol, sulfonic acid, phosphoric acid, sulfonamide, sulfonylimide, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene, as well as acidic groups such as alcohol hydroxyl groups.

[0568] Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) or a sulfonic acid group.

[0569] As a detaching group that is released by the action of an acid, examples include groups represented by general formulas (Y1) to (Y4).

[0570] General formula (Y1): -C(Rx1)(Rx2)(Rx3)

[0571] General formula (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0572] General formula (Y3): -C(R) 36 (R) 37 (OR) 38 )

[0573] General formula (Y4): -C(Rn)(H)(Ar)

[0574] In general formulas (Y1) and (Y2), Rx1 to Rx3 independently represent alkyl (straight-chain or branched) or cycloalkyl (monocyclic or polycyclic), alkenyl (straight-chain or branched) or aryl (monocyclic or polycyclic). Furthermore, when all of Rx1 to Rx3 are alkyl (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl.

[0575] Preferably, Rx1 to Rx3 represent straight-chain or branched alkyl groups, and more preferably, Rx1 to Rx3 represent straight-chain alkyl groups.

[0576] Two of Rx1 to Rx3 can also be bonded to form a single ring or multiple rings.

[0577] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0578] As for the cycloalkyl groups Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are preferred.

[0579] As for the aryl group of Rx1 to Rx3, it is preferred to have 6 to 10 carbon atoms, such as phenyl, naphthyl and anthracene.

[0580] As for the alkenyl group of Rx1 to Rx3, vinyl is preferred.

[0581] The ring formed by the two bonds of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by the two bonds of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl or adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0582] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene.

[0583] The group represented by the general formula (Y1) or (Y2) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0584] In general formula (Y3), R 36 ~R 38 Each can be used independently to represent a hydrogen atom or a monovalent organic group. R 37 With R 38 They can bond with each other to form rings. Examples of monovalent organic groups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R 36 Hydrogen atoms are preferred.

[0585] Furthermore, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups may also include groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups. For example, in the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups, for instance, one or more of the methylene groups may be substituted with groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups.

[0586] Furthermore, R 38 It can bond with another substituent in the main chain of the repeating unit to form a ring. R 38 The group formed by bonding with another substituent in the main chain of the repeating unit is preferably an alkylene group such as methylene.

[0587] As the general formula (Y3), it is preferred to be a group represented by the following formula (Y3-1).

[0588] [Chemical Formula 29]

[0589]

[0590] Here, L1 and L2 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, or groups formed by combining them (e.g., groups formed by combining alkyl and aryl).

[0591] M represents a single bond or a divalent linker.

[0592] Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (e.g., a group composed of alkyl and cycloalkyl groups).

[0593] In alkyl and cycloalkyl groups, for example, one of the methylene groups can be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0594] In addition, it is preferred that one of L1 and L2 is a hydrogen atom and the other is an alkyl, cycloalkyl, aryl, or a group composed of alkylene and aryl groups.

[0595] At least two of Q, M and L1 can be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0596] From the viewpoint of miniaturizing the pattern, L2 is preferably a secondary alkyl or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, or norbornyl, while examples of tertiary alkyl groups include tert-butyl or adamantyl. In these cases, the increased Tg (glass transition temperature) and activation energy ensure film strength and suppress blurring.

[0597] In general formula (Y4), Ar represents an aromatic cycloalgyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0598] From the viewpoint of excellent acid decomposability of repeating units, it is also preferable that when the non-aromatic ring is directly bonded to the polar group (or its residue) in the detachment group of the protecting polar group, the ring member atom in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) does not have halogen atoms such as fluorine atoms as substituents.

[0599] Furthermore, the detaching group that is released by the action of acid can also be 2-cyclopentenyl with a substituent (alkyl, etc.) such as 3-methyl-2-cyclopentenyl, and cyclohexyl with a substituent (alkyl, etc.) such as 1,1,4,4-tetramethylcyclohexyl.

[0600] As a repeating unit having an acid-decomposable group, it is also preferred to be a repeating unit represented by the general formula (A).

[0601] [Chemical Formula 30]

[0602]

[0603] L1 represents a divalent linker that may have a fluorine or iodine atom; R1 represents a fluorine atom, an iodine atom, an alkyl group that may have a fluorine or iodine atom, an aryl group that may have a fluorine or iodine atom, or a hydrogen atom; and R2 represents a released group that may have a fluorine or iodine atom and can be released by acid action. At least one of L1, R1, and R2 has a fluorine or iodine atom.

[0604] L1 represents a divalent linker that can have either a fluorine or an iodine atom. Examples of divalent linkers that can have either a fluorine or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that can have either a fluorine or an iodine atom (e.g., alkylene, cycloalkylene, alkenyl, arylene, etc.), and linkers formed by linking multiple of these. Among these, -CO- or -arylene-alkylene groups having either a fluorine or an iodine atom are preferred as L1.

[0605] As an arylene group, phenylene is preferred.

[0606] The alkylene group can be linear or branched. There is no particular limitation on the number of carbon atoms in the alkylene group, but it is preferably 1 to 10, more preferably 1 to 3.

[0607] There is no particular limitation on the total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine or iodine atoms, but it is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0608] R1 represents a fluorine atom, an iodine atom, an alkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, or a hydrogen atom.

[0609] Alkyl groups can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in an alkyl group, but it is preferably 1 to 10, more preferably 1 to 3.

[0610] There is no particular limitation on the total number of fluorine atoms and iodine atoms contained in the alkyl group having fluorine or iodine atoms, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0611] The aforementioned alkyl groups may also contain heteroatoms such as oxygen atoms other than halogen atoms.

[0612] R2 represents a detached radical that is released by the action of an acid and can have either a fluorine or iodine atom.

[0613] Among them, groups represented by general formulas (Z1) to (Z4) can be cited as detaching groups.

[0614] General formula (Z1): -C(Rx) 11 (Rx) 12 (Rx) 13 )

[0615] General formula (Z2): -C(=O)OC(Rx) 11 (Rx) 12 (Rx) 13 )

[0616] General formula (Z3): -C(R) 136 (R) 137 (OR) 138 )

[0617] General formula (Z4): -C(Rn1)(H)(Ar1)

[0618] In general formulas (Z1) and (Z2), Rx 11 ~Rx 13 Each can independently represent an alkyl group (straight-chain or branched) that may have fluorine or iodine atoms, a cycloalkyl group (monocyclic or polycyclic) that may have fluorine or iodine atoms, an alkenyl group (straight-chain or branched) that may have fluorine or iodine atoms, or an aryl group (monocyclic or polycyclic) that may have fluorine or iodine atoms. Additionally, when Rx... 11 ~Rx 13 When all components are alkyl groups (linear or branched), Rx is preferred. 11 ~Rx 13 At least two of them are methyl groups.

[0619] Rx 11 ~Rx 13 Except for the fact that it can have fluorine or iodine atoms, it is the same as Rx1 to Rx3 in (Y1) and (Y2) above, and is the same as the definition and preferred range of alkyl, cycloalkyl, alkenyl and aryl.

[0620] In general formula (Z3), R 136 ~R 138 Each can independently represent a hydrogen atom or a monovalent organic group that may have a fluorine or iodine atom. R 137 With R 138They can bond together to form a ring. Examples of monovalent organic groups that can have fluorine or iodine atoms include alkyl groups that can have fluorine or iodine atoms, cycloalkyl groups that can have fluorine or iodine atoms, aryl groups that can have fluorine or iodine atoms, aralkyl groups that can have fluorine or iodine atoms, and groups formed by combining them (e.g., a group formed by combining an alkyl group that can have fluorine or iodine atoms and a cycloalkyl group that can have fluorine or iodine atoms).

[0621] In addition to fluorine and iodine atoms, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups may also contain heteroatoms such as oxygen atoms. That is, for example, one of the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups, such as the methylene group, may be substituted by a group having heteroatoms such as oxygen atoms or carbonyl groups.

[0622] Furthermore, R 138 It can bond with another substituent in the main chain of the repeating unit to form a ring. In this case, R... 138 The group formed by bonding with another substituent in the main chain of the repeating unit is preferably an alkylene group such as methylene.

[0623] As the general formula (Z3), it is preferably a group represented by the following formula (Z3-1).

[0624] [Chemical Formula 31]

[0625]

[0626] Here, L 11 and L 12 Each of these groups can independently represent a hydrogen atom; may contain an alkyl group having a heteroatom selected from fluorine, iodine, and oxygen atoms; may contain a cycloalkyl group having a heteroatom selected from fluorine, iodine, and oxygen atoms; may contain an aryl group having a heteroatom selected from fluorine, iodine, and oxygen atoms; or a group formed by combining these groups (for example, a group formed by combining an alkyl group having a heteroatom selected from fluorine, iodine, and oxygen atoms with a cycloalkyl group having a heteroatom selected from fluorine, iodine, and oxygen atoms).

[0627] M1 represents a single bond or a divalent linker.

[0628] Q1 indicates an alkyl group that may have heteroatoms selected from fluorine, iodine, and oxygen atoms; a cycloalkyl group that may have heteroatoms selected from fluorine, iodine, and oxygen atoms; an aryl group; an amino group; an ammonium group; a mercapto group; a cyano group; an aldehyde group; or a group composed of these groups (e.g., a group composed of an alkyl group that may have heteroatoms selected from fluorine, iodine, and oxygen atoms and a cycloalkyl group that may have heteroatoms selected from fluorine, iodine, and oxygen atoms).

[0629] In the general formula (Y4), Ar1 represents an aromatic cyclic group that may have fluorine or iodine atoms. Rn1 represents an alkyl group that may have fluorine or iodine atoms, a cycloalkyl group that may have fluorine or iodine atoms, or an aryl group that may have fluorine or iodine atoms. Rn1 and Ar1 can bond with each other to form a non-aromatic ring.

[0630] As a repeating unit having an acid-decomposable group, it is also preferred to be a repeating unit represented by the general formula (AI).

[0631] [Chemical Formula 32]

[0632]

[0633] In the general formula (AI),

[0634] Xa1 represents a hydrogen atom or an alkyl group that may have substituents.

[0635] T represents a single bond or a divalent linker.

[0636] Rx1 to Rx3 independently represent alkyl (straight-chain or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (straight-chain or branched), or aryl (monocyclic or polycyclic) groups. When all of Rx1 to Rx3 are alkyl (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups.

[0637] Two of Rx1 to Rx3 can also be bonded to form monocyclic or polycyclic (monocyclic or polycyclic cycloalkyl groups).

[0638] As an alkyl group represented by Xa1, which can have substituents, examples include methyl groups or groups consisting of -CH2-R groups. 11 The group indicated by R. 11 The organic group representing a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group can be exemplified by alkyl groups having 5 or fewer carbon atoms, acyl groups having 5 or fewer carbon atoms, and alkoxy groups having 5 or fewer carbon atoms, preferably alkyl groups having 3 or fewer carbon atoms, and more preferably methyl groups. The lower limit for the number of carbon atoms in the aforementioned alkyl groups is preferably 1 or more. As Xa1, hydrogen atoms, methyl groups, trifluoromethyl groups, or hydroxymethyl groups are preferred.

[0639] Examples of divalent linkers for T include alkylene groups, aromatic cycloalkanes, -COO-Rt- groups, and -O-Rt- groups. In these formulas, Rt represents an alkylene group or a cycloalkylene group.

[0640] 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.

[0641] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0642] As for the cycloalkyl groups Rx1 to Rx3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl.

[0643] As for the aryl group of Rx1 to Rx3, it is preferred to have 6 to 10 carbon atoms, such as phenyl, naphthyl and anthracene.

[0644] As for the alkenyl group of Rx1 to Rx3, vinyl is preferred.

[0645] The cycloalkyl group formed by the bonding of two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. In addition, polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are also preferred. Among them, monocyclic cycloalkyl groups with 5 to 6 carbon atoms are preferred.

[0646] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene.

[0647] The repeating unit represented by the general formula (AT) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0648] When the above-mentioned groups have 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 substituents is preferably 8 or less. The lower limit is preferably 1 or more.

[0649] As the repeating unit represented by the general formula (AI), the acid-degradable tertiary alkyl methacrylate repeating unit is preferred (Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond repeating unit).

[0650] The content of repeating units having acid-degradable groups is preferably 15 to 80 mol% relative to all repeating units in resin (A), more preferably 20 to 70 mol%, and even more preferably 20 to 65 mol%.

[0651] The following are specific examples of repeating units having acid-degradable groups, but the present invention is not limited thereto. Furthermore, in the formula, Xa1 represents any one of H, F, CH3, CF3, and CH2OH, and Rxa and Rxb independently represent straight-chain or branched alkyl groups having 1 to 5 carbon atoms.

[0652] [Chemical Formula 33]

[0653]

[0654] [Chemical Formula 34]

[0655]

[0656] [Chemical Formula 35]

[0657]

[0658] [Chemical Formula 36]

[0659]

[0660] [Chemical Formula 37]

[0661]

[0662] Resin (A) may contain repeating units having acid-degradable groups containing unsaturated bonds.

[0663] As a repeating unit having an acid-degrading group containing an unsaturated bond, it is preferably a repeating unit represented by the general formula (B).

[0664] [Chemical Formula 38]

[0665]

[0666] In general formula (B),

[0667] Xb represents a hydrogen atom, a halogen atom, or an alkyl group that may have substituents.

[0668] L represents a single bond or a divalent linker that may have substituents.

[0669] Ry1 to Ry3 independently represent linear, branched alkyl, monocyclic, polycyclic cycloalkyl, alkenyl, alkynyl, monocyclic or polycyclic aryl groups. At least one of Ry1 to Ry3 represents an alkenyl, alkynyl, monocyclic or polycyclic cycloalkenyl, or monocyclic or polycyclic aryl group.

[0670] Two of Ry1 to Ry3 can also bond together to form monocyclic or polycyclic compounds (monocyclic or polycyclic cycloalkyl, cycloalkenyl, etc.).

[0671] As an alkyl group represented by Xb, which can have substituents, examples include methyl or alkyl groups represented by -CH2-R. 11 The group indicated by R. 11 The organic group representing a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group can be exemplified by, for example, an alkyl group with 5 or fewer carbon atoms that can be substituted by a halogen atom, an acyl group with 5 or fewer carbon atoms that can be substituted by a halogen atom, and an alkoxy group with 5 or fewer carbon atoms that can be substituted by a halogen atom. Preferably, it is an alkyl group with 3 or fewer carbon atoms, and more preferably, it is a methyl group. The lower limit for the number of carbon atoms is preferably 1 or more. As Xb, it is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0672] Examples of divalent linking groups that can have L substituents include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In these formulas, Rt represents an alkylene group, a cycloalkylene group, or an aromatic cyclic group, preferably an aromatic cyclic group.

[0673] As L, it is preferably -Rt- group, -CO- group, -COO-Rt-CO- group or -Rt-CO- group. Rt may have substituents such as halogen atom, hydroxyl group, alkoxy group or the like. It is preferably an aromatic group.

[0674] The alkyl groups of Ry1 to Ry3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0675] As for the cycloalkyl groups of Ry1 to Ry3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are preferred.

[0676] As for the aryl groups of Ry1 to Ry3, aryl groups with 6 to 10 carbon atoms are preferred, such as phenyl, naphthyl and anthracene.

[0677] As for the alkenyl group of Ry1 to Ry3, vinyl is preferred.

[0678] The acetylene group is preferred as the alkynyl group of Ry1 to Ry3.

[0679] As for the cycloalkenyl groups of Ry1 to Ry3, it is preferable that the structure contains a double bond in part of the cycloalkyl group of a monocyclic ring such as cyclopentyl or cyclohexyl.

[0680] The cycloalkyl group formed by the bonding of two of Ry1 to Ry3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. In addition, polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are also preferred. Among them, monocyclic cycloalkyl groups with 5 to 6 carbon atoms are preferred.

[0681] In the cycloalkyl or cycloalkenyl groups formed by the bonding of two bonds in Ry1 to Ry3, for example, one of the methylene groups constituting the ring may be replaced by a group having heteroatoms such as oxygen atoms, carbonyl groups, -SO2- groups, -SO3- groups, or vinylidenes, or combinations thereof. Furthermore, in these cycloalkyl or cycloalkenyl groups, one or more of the ethylidenes in the cycloalkane or cycloalkene ring may be replaced by vinylene.

[0682] The repeating unit represented by general formula (B) is preferably, for example, Ry1 is methyl, ethyl, vinyl, allyl or aryl, and Ry2 is bonded to Rx3 to form the above-mentioned cycloalkyl or cycloalkenyl.

[0683] When the above-mentioned groups have 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. The lower limit for the number of carbon atoms is preferably 1 or more.

[0684] As repeating units represented by general formula (B), the preferred repeating units are acid-degradable tertiary methacrylate repeating units (Xb represents a hydrogen atom or methyl, and L represents a -CO- group repeating unit), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (Xh represents a hydrogen atom or methyl, and L represents a phenyl repeating unit), and acid-degradable styrene carboxylic acid tertiary ester repeating units (Xb represents a hydrogen atom or methyl, and L represents a -Rt-CO- group (Rt is an aromatic group) repeating units).

[0685] The content of repeating units having acid-degradable groups containing unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in resin (A). Furthermore, as an upper limit, it is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less.

[0686] The following are specific examples of repeating units having acid-degrading groups containing unsaturated bonds, but the present invention is not limited thereto. Additionally, in the formula, Xb and L1 represent any of the substituents and linking groups described above, Ar represents an aromatic group, R represents a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acyloxy, cyano, nitro, amino, halogen atom, ester (-OCOR"' or -COOR"': R"' is an alkyl or fluorinated alkyl with 1 to 20 carbon atoms), or a carboxyl group, etc., R' represents a straight-chain, branched alkyl, monocyclic, polycyclic cycloalkyl, alkenyl, alkynyl, or monocyclic or polycyclic aryl, Q represents a group having heteroatoms such as oxygen atoms, carbonyl, -SO2-, -SO3-, etc., vinylidene, or combinations thereof, and n and m represent integers of 0 or more.

[0687] [Chemical Formula 39]

[0688]

[0689] [Chemical Formula 40]

[0690]

[0691] [Chemical Formula 41]

[0692]

[0693] [Chemical Formula 42]

[0694]

[0695] Resin (A) may also contain repeating units other than those described above.

[0696] For example, resin (A) may also contain at least one repeating unit selected from group A and / or at least one repeating unit selected from group B.

[0697] Group A: A group consisting of the following repeating units (20) to (29).

[0698] (20) Repeating units with acid groups, as described later

[0699] (21) Repeating units with fluorine or iodine atoms, as described later.

[0700] (22) Repeating units having lactone, sulcinolone, or carbonate groups as described later

[0701] (23) The repeating unit with photoacid-generating group described later

[0702] (24) Repeating units described later by general formula (V-1) or general formula (V-2) below.

[0703] (25) The repeating unit represented by equation (A) as described later

[0704] (26) The repeating unit represented by equation (B) as described later

[0705] (27) The repeating unit represented by equation (C) as described later

[0706] (28) The repeating unit represented by equation (D) as described later

[0707] (29) The repeating unit represented by equation (E) as described later

[0708] Group B: Groups that include the repeating units of (30) to (32) below.

[0709] (30) The repeating unit described below having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano and alkali-soluble groups.

[0710] (31) The repeating unit with an alicyclic hydrocarbon structure and which does not exhibit acid decomposition ability, as described later.

[0711] (32) The repeating unit described later that does not have either a hydroxyl or a cyano group and is represented by general formula (III)

[0712] When the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for EUV, the resin (A) preferably has at least one repeating unit selected from the group A above.

[0713] Furthermore, when the composition is used as a photosensitive or radiosensitive linear resin composition for EUV, the resin (A) preferably contains at least one of fluorine atoms and iodine atoms. When the resin (A) contains both fluorine atoms and iodine atoms, the resin (A) may have one repeating unit containing both fluorine atoms and iodine atoms, or the resin (A) may contain both repeating units containing fluorine atoms and repeating units containing iodine atoms.

[0714] Furthermore, when the composition is used as a photosensitive or radiosensitive linear resin composition for EUV, the resin (A) preferably contains repeating units having aromatic groups.

[0715] When the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, the resin (A) preferably has at least one repeating unit selected from group B above.

[0716] Furthermore, when the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, the resin (A) preferably does not contain either fluorine atoms or silicon atoms.

[0717] Furthermore, when the composition is used as a photosensitive or radiosensitive linear resin composition for ArF, the resin (A) preferably does not have aromatic groups.

[0718] (Repeating units with acid groups)

[0719] Resin (A) may also contain repeating units with acid groups.

[0720] As an acid group, an acid group with a pKa of 13 or less is preferred. The acid dissociation constant of the above-mentioned acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10, as described above.

[0721] As an acid group, it is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.

[0722] When resin (A) has acid groups with a pKa of 13 or less, the content of acid groups in resin (A) is not particularly limited, but is mostly 0.2 to 6.0 mmol / g. Preferably, it is 0.8 to 6.0 mmol / g, more preferably 1.2 to 5.0 mmol / g, and even more preferably 1.6 to 4.0 mmol / g. If the content of acid groups is within the above range, development proceeds well, and the resulting pattern shape and resolution are excellent.

[0723] Furthermore, in the aforementioned hexafluoroisopropanol group, one or more (preferably one to two) fluorine atoms can be substituted by groups other than fluorine atoms (such as alkoxycarbonyl groups). The resulting -C(CF3)(OH)-CF2- is also preferably an acid group. Additionally, one or more fluorine atoms can be substituted by groups other than fluorine atoms to form a ring containing -C(CF3)(OH)-CF2-.

[0724] The repeating unit having an acid group is preferably a repeating unit different from the repeating units described below, including: repeating units having a structure in which a polar group is detached by the action of the acid described above and protected by a detaching group; and repeating units having a lactone group, a sulcinolone group or a carbonate group, as described later.

[0725] Repeating units with acid groups can have fluorine or iodine atoms.

[0726] As a repeating unit having an acid group, the repeating unit represented by formula (B) is preferred.

[0727] [Chemical Formula 43]

[0728]

[0729] R3 represents a hydrogen atom or an organic group that may have a 1-valent charge, such as a fluorine atom or an iodine atom.

[0730] The preferred organic group is a monovalent group that may have fluorine or iodine atoms, and is represented by -L4-R8. L4 represents a single bond or an ester group. R8 represents an alkyl group that may have fluorine or iodine atoms, a cycloalkyl group that may have fluorine or iodine atoms, an aryl group that may have fluorine or iodine atoms, or a combination thereof.

[0731] R4 and R5 represent hydrogen, fluorine, iodine, or alkyl groups that may have fluorine or iodine atoms, respectively.

[0732] L2 represents a single bond or ester group.

[0733] L3 represents an aromatic hydrocarbon cyclic group with a valence of (n+m+1) or an alicyclic hydrocarbon cyclic group with a valence of (n+m+1). Examples of aromatic hydrocarbon cyclic groups include benzene and naphthyl groups. Examples of alicyclic hydrocarbon cyclic groups include monocyclic and polycyclic groups, such as cycloalkyl groups.

[0734] R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Additionally, when R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon cyclic group with a (n+m+1) valence.

[0735] R7 represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0736] m represents an integer greater than or equal to 1. m is preferably an integer from 1 to 3, and more preferably an integer from 1 to 2.

[0737] n represents an integer of 0 or 1 or higher. n is preferably an integer between 1 and 4.

[0738] In addition, (n+m+1) is preferably an integer from 2 to 5.

[0739] The following repeating units can be cited as examples of repeating units with acid groups.

[0740] [Chemical Formula 44]

[0741]

[0742] As a repeating unit having an acid group, it is also preferred to be a repeating unit represented by the following general formula (I).

[0743] [Chemical Formula 45]

[0744]

[0745] In general formula (I),

[0746] R 41 R 42 and R 43Each of these groups independently represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group, or alkoxycarbonyl group. Wherein, R... 42 It can bond with Ar4 to form a ring, at which point R 42 Indicates a single bond or an alkylene group.

[0747] X4 indicates a single bond, -COO-, or -CONR. 64 -, R 64 It represents a hydrogen atom or an alkyl group.

[0748] L4 indicates a single bond or alkylene group.

[0749] Ar4 represents an aromatic ring group with an (n+1) valence, when it is combined with R 42 When bonded to form a ring, it represents an aromatic ring group with an (n+2) valence.

[0750] n represents an integer from 1 to 5.

[0751] R in general formula (I) 41 R 42 and R 43 The alkyl group is preferably an alkyl group with 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl. More preferably, it is an alkyl group with 8 or fewer carbon atoms, and even more preferably, it is an alkyl group with 3 or fewer carbon atoms. The lower limit for the number of carbon atoms is preferably 1 or more.

[0752] R in general formula (I) 41 R 42 and R 43 The cycloalkyl group can be monocyclic or polycyclic. Preferably, it is a monocyclic cycloalkyl group with 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl.

[0753] R in general formula (I) 41 R 42 and R 43 The halogen atom can be fluorine, chlorine, bromine, or iodine, with fluorine being the preferred atom.

[0754] R in general formula (I) 41 R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group is preferably a derivative of the above-mentioned R. 41 R 42 and R 43 The alkyl group in the text is the same as the alkyl group in the text.

[0755] Preferred substituents among the aforementioned groups include, for example, alkyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxyl, carboxyl, halogen, alkoxy, thioether, acyl, acyloxy, alkoxycarbonyl, cyano, and nitro groups. The substituent preferably has 8 or fewer carbon atoms. The lower limit for the number of carbon atoms is preferably 1 or more.

[0756] Ar4 represents an aromatic cyclic group with an (n+1) valence. For an n of 1, a divalent aromatic cyclic group is preferably an arylene group with 6 to 18 carbon atoms, such as phenylene, tolylene group, naphthylene, or anthracene; or a divalent aromatic cyclic group containing heterocycles, such as thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, or thiazole ring. Furthermore, the aforementioned aromatic cyclic groups may have substituents.

[0757] As a specific example of an aromatic cyclic group with a valence of (n+1) when n is an integer greater than 2, a group formed by removing (n-1) arbitrary hydrogen atoms from the above specific examples of a divalent aromatic cyclic group can be given.

[0758] (n+1) valence aromatic cyclic groups can also have substituents.

[0759] Substituents that can be present as the above-mentioned alkyl, cycloalkyl, alkoxycarbonyl, alkylene, and (n+1) valence aromatic cyclic groups include, for example, R in general formula (I). 41 R 42 and R 43 The examples listed include alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy alkoxy groups; aryl groups such as phenyl groups; etc.

[0760] As represented by X4 -CONR 64 -(R 64 R in (representing hydrogen atom or alkyl group) 64 Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, which have 20 or fewer carbon atoms, and preferably alkyl groups with 8 or fewer carbon atoms. The lower limit for the number of carbon atoms is preferably 1 or more.

[0761] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0762] The alkylene group in L4 is preferably an alkylene group with 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene.

[0763] Ar4 is preferably an aromatic cyclic group with 6 to 18 carbon atoms, and more preferably a benzene cyclic group, a naphthyl cyclic group, or a biphenylene cyclic group.

[0764] The repeating unit represented by the general formula (T) preferably has a hydroxystyrene structure. That is, Ar4 is preferably a benzene ring group.

[0765] As a repeating unit represented by general formula (I), it is preferred to be a repeating unit represented by the following general formula (1).

[0766] [Chemical Formula 46]

[0767]

[0768] In general formula (1),

[0769] A represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group.

[0770] R represents a halogen atom, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, alkoxy, alkylcarbonyloxy, alkylsulfonyloxy, alkoxycarbonyl, or aryloxycarbonyl. When multiple Rs are present, they can be the same or different. When multiple Rs are present, they can collectively form a ring. Hydrogen atoms are preferred as R.

[0771] a represents an integer from 1 to 3.

[0772] b represents an integer from 0 to (5-a).

[0773] The following examples illustrate repeating units with acid groups. In the formula, a represents 1 or 2.

[0774] [Chemical Formula 47]

[0775]

[0776] [Chemical Formula 48]

[0777]

[0778] [Chemical Formula 49]

[0779]

[0780] Furthermore, among the repeating units described above, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0781] [Chemical Formula 50]

[0782]

[0783] [Chemical Formula 51]

[0784]

[0785] The content of repeating units having acid groups is preferably 10 to 70 mol% relative to all repeating units in resin (A), more preferably 10 to 60 mol%, and even more preferably 10 to 50 mol%.

[0786] (Repeating units containing fluorine or iodine atoms)

[0787] Unlike the aforementioned <repeating units with acid-decomposing groups> and <repeating units with acid groups>, resin (A) may also contain repeating units with fluorine or iodine atoms. Furthermore, the <repeating units with fluorine or iodine atoms> mentioned here are preferably different from other types of repeating units belonging to group A, such as <repeating units with lactone, sulopentalide, or carbonate groups> and <repeating units with photoacid-generating groups>, which will be described later.

[0788] As a repeating unit having fluorine or iodine atoms, the repeating unit represented by formula (C) is preferred.

[0789] [Chemical Formula 52]

[0790]

[0791] L5 represents a single bond or ester group.

[0792] R9 represents a hydrogen atom or an alkyl group that may have a fluorine atom or an iodine atom.

[0793] R 10 It represents a hydrogen atom, an alkyl group that may have a fluorine atom or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, or a group composed of these.

[0794] The following examples illustrate repeating units having fluorine or iodine atoms.

[0795] [Chemical Formula 53]

[0796]

[0797] The content of repeating units having fluorine or iodine atoms is preferably 0 to 60 mol% relative to all repeating units in resin (A), more preferably 5 to 60 mol%, and even more preferably 10 to 60 mol%.

[0798] Furthermore, as mentioned above, since repeating units containing fluorine or iodine atoms do not include repeating units with acid-decomposing groups or repeating units with acid groups, the aforementioned content of repeating units containing fluorine or iodine atoms also refers to the content of repeating units containing fluorine or iodine atoms other than repeating units with acid-decomposing groups or repeating units with acid groups.

[0799] The total content of repeating units containing at least one of fluorine atoms and iodine atoms in the repeating units of resin (A) is preferably 1 to 100 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 60 mol%, relative to all repeating units of resin (A).

[0800] In addition, as repeating units containing at least one of fluorine atoms and iodine atoms, examples include repeating units having fluorine atoms or iodine atoms and having acid-decomposing groups, repeating units having fluorine atoms or iodine atoms and having acid groups, and repeating units having fluorine atoms or iodine atoms.

[0801] (Repeating units with lactone, sulcinolone, or carbonate groups)

[0802] Resin (A) may contain repeating units having at least one selected from lactone, sulopentalide, and carbonate groups (hereinafter also collectively referred to as "repeating units having lactone, sulopentalide, or carbonate groups").

[0803] Repeating units having lactone, sulcinolone, or carbonate groups are preferably free of acid groups such as hexafluoropropanol groups.

[0804] As the lactone or sulfonolactone group, it is sufficient to have a lactone structure or a sulfonolactone structure. The lactone structure or sulfonolactone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sulfonolactone structure. More preferably, it is a structure in which other ring structures are fused to the 5- to 7-membered ring lactone structure in the form of a bicyclic or spirocyclic structure, or a structure in which other ring structures are fused to the 5- to 7-membered ring sulfonolactone structure in the form of a bicyclic or spirocyclic structure.

[0805] The resin (A) preferably comprises repeating units having a lactone group or a sulfonolactone group, formed by removing one or more hydrogen atoms from the ring member atoms of a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21) or a sulfonolactone structure represented by any one of the following general formulas (SL1-1) to (SL1-3).

[0806] Furthermore, lactone or sulfonyl groups can be directly bonded to the main chain. For example, the ring-membered atoms of the lactone or sulfonyl groups can form the main chain of resin (A).

[0807] [Chemical Formula 54]

[0808]

[0809] The aforementioned lactone or sulopentalide structure may have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 4 to 7 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 1 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple Rb2 groups can be different, and the multiple Rb2 groups can bond together to form a ring.

[0810] As a repeating unit comprising a group having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-21) or a sulfonyl lactone structure represented by any one of the general formulas (SL1-1) to (SL1-3), for example, repeating units represented by the following general formula (AI) can be cited.

[0811] [Chemical Formula 55]

[0812]

[0813] In the general formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

[0814] Preferred substituents that an alkyl group can have as Rb0 include hydroxyl groups and halogen atoms.

[0815] Examples of halogen atoms that can be represented by Rb0 include fluorine, chlorine, bromine, and iodine. Rb0 is preferably represented by hydrogen or methyl.

[0816] Ab represents a single bond, an alkylene group, a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group composed of combinations thereof. Preferably, it is a single bond or a linker represented by -Ab1-CO2-. Ab1 is a straight-chain or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably methylene, ethylene, cyclohexylene, adamantylene, or norbornylene.

[0817] V represents a group formed by removing one hydrogen atom from the ring-membered atom of a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-21), or a group formed by removing one hydrogen atom from the ring-membered atom of a sulfonyl lactone structure represented by any one of the general formulas (SL1-1) to (SL1-3).

[0818] When an optical isomer exists in a repeating unit having a lactone group or a sulopentalide group, any optical isomer can be used. Furthermore, a single optical isomer can be used alone, or multiple optical isomers can be used in combination. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, more preferably 95 or higher. The upper limit is preferably 100 or lower.

[0819] As a carbonate group, a cyclic carbonate group is preferred.

[0820] As a repeating unit having a cyclic carbonate group, it is preferably a repeating unit represented by the following general formula (A-1).

[0821] [Chemical Formula 56]

[0822]

[0823] In general formula (A-1), R A 1 It represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably methyl).

[0824] n represents an integer greater than or equal to 0.

[0825] R A 2 This represents a substituent. When n is 2 or more, there exist multiple Rsub. A 2 They can be the same or different.

[0826] A represents a single bond or a divalent linker. Preferably, the divalent linker is an alkylene group, a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group formed by combining these.

[0827] Z represents a group that, together with a group represented by -O-CO-O- in the formula, forms a monocyclic or polycyclic atom.

[0828] The following examples illustrate repeating units having lactone, sulcinolone, or carbonate groups.

[0829] [Chemical Formula 57]

[0830] (In the formula, Rx represents H, CH3, CH2OH or CF3)

[0831]

[0832] [Chemical Formula 58]

[0833] (In the formula, Rx represents H, CH3, CH2OH or CF3)

[0834]

[0835] [Chemical Formula 59]

[0836] (In the formula, Rx represents H, CH3, CH2OH or CF3)

[0837]

[0838] The content of repeating units having lactone, sulopentalide, or carbonate groups relative to all repeating units in resin (A) is preferably 1 to 70 mol%, more preferably 5 to 65 mol%, and even more preferably 5 to 60 mol%.

[0839] (Repeating unit with photoacid-generating group)

[0840] Resin (A) may also contain repeating units having groups that generate acid upon irradiation by photochemical rays or radiation (hereinafter also referred to as "photoacid-generating groups") as repeating units other than those described above.

[0841] At this point, the repeating unit having the photoacid-generating group can be considered equivalent to the compound that produces acid by irradiation with photochemical rays or radiation (hereinafter also referred to as "photoacid-generating agent").

[0842] As such a repeating unit, for example, a repeating unit represented by the following general formula (4) can be cited.

[0843] [Chemical Formula 60]

[0844]

[0845] R 41 This indicates a hydrogen atom or a methyl group. L 41 Indicates a single bond or a divalent linker. L 42 Represents a binary linker. R 40 This indicates a structural site where acid is produced in the side chain through decomposition by photochemical rays or radiation.

[0846] As a repeating unit represented by general formula (4), examples include the repeating unit described in paragraphs

[0094] to

[0105] of Japanese Patent Application Publication No. 2014-041327 and the repeating unit described in paragraph

[0094] of International Publication No. 2018 / 193954.

[0847] The content of repeating units having photoacid-generating groups is preferably 1 to 40 mol% relative to all repeating units in resin (A), more preferably 5 to 35 mol%, and even more preferably 5 to 30 mol%.

[0848] (Repeating units represented by general formula (V-1) or (V-2))

[0849] Resin (A) may also have repeating units represented by the following general formula (V-1) or the following general formula (V-2).

[0850] The repeating unit represented by the following general formula (V-1) and the following general formula (V-2) is preferably a repeating unit that is different from the repeating unit described above.

[0851] [Chemical Formula 61]

[0852]

[0853] In the formula,

[0854] R6 and R7 independently represent a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR or -COOR: R is an alkyl or fluoroalkyl group with 1 to 6 carbon atoms) or carboxyl group. As an alkyl group, a straight-chain, branched or cyclic alkyl group with 1 to 10 carbon atoms is preferred.

[0855] n3 represents an integer from 0 to 6.

[0856] n4 represents an integer from 0 to 4.

[0857] X4 represents a methylene group, an oxygen atom, or a sulfur atom.

[0858] The following examples illustrate repeating units represented by the general formula (V-1) or (V-2).

[0859] [Chemical Formula 62]

[0860]

[0861] (Repetitive units used to reduce the mobility of the main chain)

[0862] From the viewpoint of suppressing excessive diffusion of generated acid or pattern breakdown during development, resin (A) preferably has a high glass transition temperature (Tg). Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. In addition, excessively high Tg will lead to a decrease in the dissolution rate in the developer, so Tg is preferably below 400°C, more preferably below 350°C.

[0863] In addition, in this specification, the glass transition temperature (Tg) of polymers such as resin (A) is calculated by the following method. First, the Tg of the homopolymer composed only of each repeating unit contained in the polymer is calculated separately using the Bicerano method. Then, the calculated Tg is referred to as the "repeating unit Tg". Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Then, the Tg of each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152 et al.), and their sum is set as the Tg (°C) of the polymer.

[0864] The Bicerano method is documented in *Prediction of polymer properties*, Marcel Dekker Inc., New York (1993), etc. Furthermore, the Tg calculation performed using the Bicerano method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0865] In order to increase the Tg of resin (A) (preferably exceeding 90°C), it is preferable to reduce the mobility of the main chain of resin (A). Methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e).

[0866] (a) Introducing bulk substituents into the main chain

[0867] (b) Introducing multiple substituents into the main chain

[0868] (c) Introducing substituents that trigger interactions between resins (CA) into the vicinity of the main chain.

[0869] (d) Formation of the main chain in the ring structure

[0870] (e) Connect the ring structure to the main chain

[0871] In addition, resin (A) preferably has repeating units with a Tg of 130°C or higher in homopolymers.

[0872] Furthermore, there are no particular restrictions on the types of repeating units with a Tg of 130°C or higher in the homopolymer, as long as the repeating unit has a Tg of 130°C or higher as calculated by the Bicerano method. Additionally, the types of functional groups in the repeating units represented by equations (A) to (E) described later correspond to repeating units with a Tg of 130°C or higher in the homopolymer.

[0873] (Repeating unit represented by equation (A))

[0874] As an example of a specific implementation of (a) above, a method of introducing the repeating unit represented by formula (A) into resin (A) can be given.

[0875] [Chemical Formula 63]

[0876]

[0877] In formula (A), R A This indicates a group with a polycyclic structure. R x This indicates a hydrogen atom, methyl, or ethyl group. A polycyclic group is a group with multiple ring structures; these ring structures may or may not be fused.

[0878] As a specific example of a repeating unit represented by formula (A), the repeating unit described in paragraphs

[0107] to

[0119] of International Publication No. 2018 / 193954 can be cited.

[0879] (Repeating unit represented by equation (B))

[0880] As an example of a specific implementation of (b) above, a method of introducing the repeating unit represented by formula (B) into resin (A) can be given.

[0881] [Chemical Formula 64]

[0882]

[0883] In equation (B), R b1 ~R b4 Each can independently represent a hydrogen atom or an organic group, R b1 ~R b4 At least two of them represent organic groups.

[0884] Furthermore, when at least one of the organic groups is a ring structure directly attached to the main chain of the repeating unit, there are no particular restrictions on the types of other organic groups.

[0885] Furthermore, when none of the organic groups are directly attached to the main chain of the repeating unit by a ring structure, at least two of the organic groups are substituents with a number of three or more constituent atoms other than hydrogen atoms.

[0886] As a specific example of a repeating unit represented by formula (B), the repeating unit described in paragraphs

[0113] to

[0115] of International Publication No. 2018 / 193954 can be cited.

[0887] (Repeating unit represented by equation (C))

[0888] As an example of a specific implementation of (c) above, a method of introducing the repeating unit represented by formula (C) into resin (A) can be given.

[0889] [Chemical Formula 65]

[0890]

[0891] In equation (C), R c1 ~R c4 Each can independently represent a hydrogen atom or an organic group, R c1 ~R c4 At least one of them is a group having hydrogen atoms with hydrogen bonding capacity of 3 or less from the main chain carbon. Preferably, it has hydrogen atoms with hydrogen bonding capacity of 2 or less (closer to the main chain side) on the basis of causing the interaction between the main chains of resin (A).

[0892] As a specific example of a repeating unit represented by formula (C), the repeating unit described in paragraphs

[0119] to

[0121] of International Publication No. 2018 / 193954 can be cited.

[0893] (Repeating unit represented by equation (D))

[0894] As an example of a specific implementation of (d) above, a method of introducing the repeating unit represented by formula (D) into resin (A) can be given.

[0895] [Chemical Formula 66]

[0896]

[0897] In formula (D), "cylic" represents a group whose main chain is formed by a ring structure. There is no particular restriction on the number of atoms constituting the ring.

[0898] As a specific example of a repeating unit represented by formula (D), the repeating unit described in paragraphs

[0126] to

[0127] of International Publication No. 2018 / 193954 can be cited.

[0899] (Repeating unit represented by equation (E))

[0900] As an example of a specific implementation of (e) above, a method of introducing the repeating unit represented by formula (E) into resin (A) can be given.

[0901] [Chemical Formula 67]

[0902]

[0903] In formula (E), Re represents a hydrogen atom or an organic group. Examples of organic groups that can have substituents include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups.

[0904] "Cylic" is a cyclic group containing carbon atoms in the main chain. There is no particular limitation on the number of atoms contained in a cyclic group.

[0905] As a specific example of a repeating unit represented by formula (E), the repeating unit described in paragraphs

[0131] to

[0133] of International Publication No. 2018 / 193954 can be cited.

[0906] The content of the repeating unit represented by formula (E) relative to all repeating units in resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more. Furthermore, as an upper limit, it is preferably 60 mol% or less, more preferably 55 mol% or less.

[0907] (A repeating unit having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano, and alkali-soluble groups)

[0908] Resin (A) may contain repeating units having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano and alkali-soluble groups.

[0909] As for the repeating units having lactone, sulfonyl, or carbonate groups in resin (A), examples of repeating units described in the above-described <Repeating units having lactone, sulfonyl, or carbonate groups> can be cited. The preferred content is also as described in the above-described <Repeating units having lactone, sulfonyl, or carbonate groups>.

[0910] Resin (A) may also contain repeating units with hydroxyl or cyano groups. This improves substrate adhesion and developer affinity.

[0911] The repeating unit having a hydroxyl or cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl or cyano group.

[0912] The repeating unit having a hydroxyl or cyano group preferably does not have an acid-degradable group. Examples of repeating units having a hydroxyl or cyano group include those described in paragraphs

[0153] to

[0158] of International Publication No. 2020 / 004306.

[0913] Resin (A) may also contain repeating units with alkali-soluble groups.

[0914] Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohols substituted with electron-withdrawing groups at the α-position (e.g., hexafluoroisopropanol groups), with carboxyl groups being preferred. By including repeating units having alkali-soluble groups in the resin (A), the resolution in contact hole applications is improved.

[0915] Examples of repeating units with alkali-soluble groups include repeating units formed from acrylic acid and methacrylic acid where the alkali-soluble groups are directly bonded to the resin backbone, or repeating units where the alkali-soluble groups are bonded to the resin backbone via linkers. Furthermore, the linkers can have monocyclic or polycyclic cyclic hydrocarbon structures.

[0916] As a repeating unit having an alkali-soluble group, it is preferably a repeating unit formed of acrylic acid or methacrylic acid.

[0917] The content of repeating units having alkali-soluble groups is preferably 0 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, relative to all repeating units in resin (A). As an upper limit, it is preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less.

[0918] The following are specific examples of repeating units having alkali-soluble groups, but the invention is not limited thereto. In the specific examples, Rx represents H, CH3, CH2OH, or CF3.

[0919] [Chemical Formula 68]

[0920]

[0921] As a repeating unit having at least one group selected from lactone, hydroxyl, cyano and alkali-soluble groups, it is preferably a repeating unit having at least two groups selected from lactone, hydroxyl, cyano and alkali-soluble groups, more preferably a repeating unit having cyano and lactone groups, and even more preferably a repeating unit having a cyano-substituted structure in the lactone structure represented by general formula (LC1-4).

[0922] (Repeating unit with an alicyclic hydrocarbon structure and not exhibiting acid decomposition properties)

[0923] Resin (A) may also contain repeating units with an alicyclic hydrocarbon structure that do not exhibit acid decomposition properties. This reduces the leaching of low-molecular-weight components from the resist film into the immersion solution during immersion exposure. Examples of such repeating units include those derived from 1-adamantane (meth)acrylate, diadamantane (meth)acrylate, tricyclodecane (meth)acrylate, or cyclohexyl (meth)acrylate.

[0924] (A repeating unit that does not have either a hydroxyl or a cyano group and is represented by general formula (III))

[0925] Resin (A) may also contain repeating units that do not have either hydroxyl or cyano groups and are represented by general formula (III).

[0926] [Chemical Formula 69]

[0927]

[0928] In general formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and not having either a hydroxyl or a cyano group.

[0929] Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.

[0930] The cyclic structure of R5 includes monocyclic hydrocarbon groups and polycyclic hydrocarbon groups. Examples of monocyclic hydrocarbon groups include cycloalkyl groups with 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) or cycloalkenyl groups with 3 to 12 carbon atoms.

[0931] As a detailed definition of each group in general formula (III) and a specific example of repeating units, the detailed definitions and repeating units described in paragraphs

[0169] to

[0173] of International Publication No. 2020 / 004306 can be cited.

[0932] (Other repeating units)

[0933] Resin (A) may also contain repeating units other than those described above.

[0934] For example, resin (A) may contain repeating units selected from repeating units having an oxathiane ring group, repeating units having an oxazorone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group.

[0935] The following is an example of such repeating units.

[0936] [Chemical Formula 70]

[0937]

[0938] In addition to the repeating structural units mentioned above, resin (A) may also have various repeating structural units for purposes such as adjusting dry etching resistance, compatibility with standard developer, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0939] As resin (A), (especially when the composition is used as a photosensitive or radiosensitive linear resin composition for ArF) it is also preferred that all repeating units are composed of (meth)acrylate repeating units. In this case, any one of the following repeating units can be used: repeating units in which all repeating units are methacrylate repeating units, repeating units in which all repeating units are acrylate repeating units, and repeating units in which all repeating units are formed from methacrylate repeating units and acrylate repeating units, wherein the acrylate repeating units are preferably 50 mol% or less of all repeating units.

[0940] Resin (A) can be synthesized using conventional methods (e.g., free radical polymerization).

[0941] As a conversion value for polystyrene based on the GPC method, the weight-average molecular weight of resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000. By setting the weight-average molecular weight of resin (A) to 1,000 to 200,000, the deterioration of heat resistance and dry etching resistance can be further suppressed. Furthermore, the deterioration of film-forming properties caused by deterioration of developability and increased viscosity can be further suppressed.

[0942] The dispersion (molecular weight distribution) of resin (A) is typically 1 to 5, preferably 1 to 3, more preferably 1.20 to 3.00, and even more preferably 1.20 to 2.00. The smaller the dispersion, the better the resolution and resist shape, and the smoother the sidewalls of the resist pattern, and the better the roughness.

[0943] In the composition of the present invention, the content of resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, relative to the total solid content of the composition.

[0944] In addition, solid components refer to components in a composition other than solvents. Any component other than solvents, even liquid components, are considered solid components.

[0945] Furthermore, one type of resin (A) may be used, or multiple types may be used in combination.

[0946] <Other photoacid-producing agents>

[0947] The resist composition may contain other photoacid generators (compounds that generate acid by exposure to photochemical rays or radiation, which are not equivalent to a specific compound). Other photoacid generators are compounds that generate acid by exposure (preferably EUV light and / or ArF exposure).

[0948] Other photoacid-generating agents can be in the form of low-molecular-weight compounds or in the form of compounds embedded in a polymer. Furthermore, both low-molecular-weight compound forms and forms embedded in a polymer can be used in combination.

[0949] When other photoacid-generating agents are in the form of low-molecular-weight compounds, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. The lower limit is preferably 50 or more.

[0950] When other photoacid generators are in the form of being embedded in a part of a polymer, they can be embedded in a part of resin (A) or in a resin different from resin (A).

[0951] In this invention, the photoacid generator is preferably in the form of a low molecular weight compound.

[0952] Other photoacid-generating agents are not particularly limited, but compounds that generate organic acids are preferred. As for the organic acids mentioned above, examples of organic acids that can be generated by specific compounds can also be given.

[0953] Other photoacid-producing agents include, for example, those derived from "M" + Y - The compound indicated by "" is a bismuth salt.

[0954] In the case of “M” + Y - In the compound indicated by ", Y represents a monovalent organic anion.

[0955] As "M" + Y - The Y in “” can be an example of a monovalent organic anion contained in the specific compound mentioned above.

[0956] In the case of “M” + Y - In the compounds represented by "", M + This represents a monovalent organic cation.

[0957] The aforementioned monovalent organic cations are preferably cations represented by the general formula (ZaI) (cation (ZaI)) or cations represented by the general formula (ZaII) (cation (ZaII)).

[0958] The cation represented by the general formula (ZaI) is different from the cation (other than Y) in the specific compound (the compound represented by general formulas (1) to (3)).

[0959] [Chemical Formula 71]

[0960]

[0961] R 204 -| + -R 205 (ZaII)

[0962] In the above general formula (ZaI),

[0963] R 201 R 202 and R 203 Each organic group can be represented independently.

[0964] As R 201 R 202 and R 203 The number of carbon atoms in the organic group is typically 1 to 30, preferably 1 to 20. Furthermore, R... 201 ~R 203 The two atoms in the ring can bond together to form a ring structure, or the ring can contain oxygen atoms, sulfur atoms, ester groups, amide groups, or carbonyl groups. As R 201 ~R 203 Two groups formed by bonding can be alkylene groups (e.g., butylene, pentylene, etc.) and -CH2-CH2-O-CH2-CH2-.

[0965] Examples of cations in the general formula (ZaI) include, for example, the cation described later (ZaI-1).

[0966] The cation (ZaI-1) is R in the above general formula (ZaI). 201 ~R 203 At least one of them is an aryl arbutin cation of aryl.

[0967] In arylsulfonium cations, R can be 201 ~R 203 All are aryl, or can be R 201 ~R 203 One part of it is aryl, and the rest is alkyl or cycloalkyl.

[0968] Furthermore, R 201 ~R 203 One of them is aryl, R 201 ~R 203 The remaining two atoms can bond together to form a ring structure, or the ring can contain oxygen atoms, sulfur atoms, ester groups, amide groups, or carbonyl groups. As R 201 ~R 203 Two groups formed by bonding in the group, for example, one or more methylene groups can be substituted by an oxygen atom, a sulfur atom, an ester group, an amide group and / or a carbonyl group (e.g., butylene, pentylene or -CH2-CH2-O-CH2-CH2-).

[0969] Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0970] The aryl group contained in the aryl sulfonium cation is preferably phenyl or naphthyl, more preferably phenyl. The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom, nitrogen atom, or sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl sulfonium cation has two or more aryl groups, the two or more aryl groups can be the same or different.

[0971] The alkyl or cycloalkyl group of the arylsulfonium cation is preferably a straight-chain alkyl group with 1 to 15 carbon atoms, a branched alkyl group with 3 to 15 carbon atoms, or a cycloalkyl group with 3 to 15 carbon atoms, for example, more preferably methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, or cyclohexyl.

[0972] R 201 ~R 203 The aryl, alkyl, and cycloalkyl groups may have substituents that are preferably alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 14 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), cycloalkylalkoxy (e.g., 3 to 15 carbon atoms), halogen (e.g., fluorine, iodine), hydroxyl, carboxyl, ester, thionyl, sulfonyl, alkylthio, or phenylthio.

[0973] The above-mentioned substituents may also have substituents where possible. For example, the above-mentioned alkyl group may have a halogen atom as a substituent to become a trifluoromethyl or other haloalkyl group.

[0974] The substituents described above are preferably combined in any way to form acid-degradable groups. An acid-degradable group is a group that decomposes to produce a polar group by the action of an acid, and preferably has a structure in which a polar group is protected by a release group that is released by the action of an acid. Examples of polar groups, release groups, and acid-degradable groups can be given from the specific compounds described above.

[0975] Other photoacid-generating agents include, for example, the following compounds.

[0976] [Chemical Formula 72]

[0977]

[0978] When the resist composition contains other photoacid-generating agents, their content is not particularly limited. However, from the viewpoint of achieving better results in this invention, the content is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, relative to the total solid content of the composition. Furthermore, the above-mentioned content is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0979] One type of photoacid generator can be used alone, or two or more types can be used.

[0980] Solvent

[0981] The resist composition may also contain a solvent.

[0982] The solvent preferably contains at least one of (M1) propylene glycol monoalkyl ether carboxylic acid ester and (M2), wherein (M2) is selected from at least one of propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone, and alkylene carbonate. Additionally, the solvent may contain components other than (M1) and (M2).

[0983] The inventors have discovered that by combining this solvent with the aforementioned resin, the coatability of the composition is improved, and patterns with fewer development defects can be formed. Although the reason is not yet clear, the inventors believe that the reason is that, due to the good balance of solubility, boiling point, and viscosity of these solvents in the aforementioned resin, uneven film thickness of the composition film and the generation of precipitates during spin coating can be suppressed.

[0984] Details of ingredients (M1) and (M2) are described in paragraphs

[0218] to

[0226] of International Publication No. 2020 / 004306.

[0985] The solvent may also contain components other than (M1) and (M2). In this case, the content of components other than (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of solvent.

[0986] The solvent content in the resist composition is preferably set to a solid component concentration of 0.5 to 30% by mass, more preferably 1 to 20% by mass. This can further improve the coatability of the resist composition.

[0987] In addition, solid components refer to all components except the solvent.

[0988] <Acid diffusion control agent>

[0989] The resist composition may further contain an acid diffusion control agent. The acid diffusion control agent acts as a quencher to capture acid generated by the photoacid generator and plays a role in controlling the diffusion of acid in the resist film.

[0990] Acid diffusion control agents can be exemplified by basic compounds.

[0991] The basic compound is preferably a compound having a structure represented by the following general formulas (A) to (E).

[0992] [Chemical Formula 73]

[0993]

[0994] In general formulas (A) and (E), R 200 R 201 and R 202 These can be the same or different, representing hydrogen atoms, alkyl groups (preferably 1 to 20 carbon atoms), cycloalkyl groups (preferably 3 to 20 carbon atoms), or aryl groups (preferably 6 to 20 carbon atoms). Here, R... 201 and R 202 They can bond together to form a ring.

[0995] Regarding the aforementioned alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.

[0996] R 203 R 204 R 205 and R 206 They can be the same or different, and they represent alkyl groups with 1 to 20 carbon atoms.

[0997] The alkyl groups in these general formulas (A) and (E) are preferably unsubstituted.

[0998] The resist composition, as an acid diffusion control agent, may contain a compound (hereinafter also referred to as "compound (PA)") that produces a compound having a proton acceptor functional group and decomposes upon irradiation by photochemical rays or radiation, thereby reducing or eliminating proton acceptor properties or transforming from proton acceptor properties to acidic properties.

[0999] A proton acceptor functional group is a functional group that has a group or electrons capable of electrostatically interacting with a proton. For example, it represents a functional group having the structure of a macrocyclic compound such as a cyclic polyether, or a functional group having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. A nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following general formula.

[1000] [Chemical Formula 74]

[1001]

[1002] As acid diffusion control agents, compounds described in paragraphs

[0238] to

[0271] of International Publication No. 2020 / 004306 can be cited.

[1003] When the resist composition contains an acid diffusion control agent, the content of the acid diffusion control agent is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, relative to the total solid content of the resist composition.

[1004] Acid diffusion control agents can be used alone or in combination with two or more.

[1005] Furthermore, when the resist composition contains a specific compound having an anion represented by any one of formulas (d1-1) to (d1-3) and / or other photoacid generators having an anion represented by any one of formulas (d1-1) to (d1-3) (hereinafter, they are also collectively referred to as "d1-type photoacid generators"), the d1-type photoacid generators can also function as acid diffusion control agents. When the resist composition contains a d1-type photoacid generator, it is also preferable that the resist composition does not actually contain an acid diffusion control agent. Here, "does not actually contain an acid diffusion control agent" means that the content of the acid diffusion control agent is 5% by mass or less relative to the total content of the d1-type photoacid generators.

[1006] Furthermore, when the resist composition contains both a d1-type photoacid generator and an acid diffusion control agent, the total content of both is preferably 1 to 30% by mass, more preferably 3 to 20% by mass.

[1007] The preferred ratio of photoacid generator to acid diffusion control agent in the resist composition is 2.0 to 300 (molar ratio). From the viewpoint of sensitivity and resolution, the molar ratio is preferably 2.0 or higher. There is no particular upper limit, but from the viewpoint of suppressing the reduction in resolution caused by the coarsening of the resist pattern over time from exposure to heat treatment, the molar ratio is preferably 300 or lower. The photoacid generator to acid diffusion control agent (molar ratio) is more preferably 2.0 to 200, and even more preferably 2.0 to 150.

[1008] As acid diffusion control agents, examples include compounds described in paragraphs

[0140] to

[0144] of Japanese Patent Application Publication No. 2013-11833 (amine compounds, amide-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds, etc.).

[1009] <Hydrophobic resin>

[1010] In addition to the resin (A) described above, the resist composition may also contain a hydrophobic resin different from resin (A).

[1011] Hydrophobic resins are preferably designed to be biased towards the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups in the molecule, nor do they need to contribute to the uniform mixing of polar and non-polar substances.

[1012] As an example of the effects of adding hydrophobic resin, the control of the static and dynamic contact angle of the resist film surface with respect to water and the suppression of outgassing can be cited.

[1013] From the viewpoint of favoring the surface layer of the film, the hydrophobic resin preferably has one or more of the following: "fluorine atoms", "silicon atoms", and "CH3 moiety contained in the side chain portion of the resin", more preferably two or more. Furthermore, the hydrophobic resin preferably has a hydrocarbon group with five or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted by the side chain.

[1014] As hydrophobic resins, examples include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306.

[1015] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, relative to the total solid content of the resist composition.

[1016] <surfactants>

[1017] Anti-corrosion compositions may also contain surfactants.

[1018] When surfactants are present, patterns with better adhesion and fewer development defects can be formed.

[1019] The surfactant is preferably a fluorinated and / or silicone surfactant.

[1020] As surfactants, examples include the compounds described in paragraphs

[0281] to

[0282] of International Publication No. 2020 / 004306.

[1021] Surfactants can be used alone or in combination with two or more.

[1022] When the resist composition contains a surfactant, the surfactant content is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, and even more preferably 0.05 to 0.5% by mass, relative to the total solid content of the composition.

[1023] <Other Additives>

[1024] The resist composition may further comprise a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in the developer (e.g., a phenolic compound with a molecular weight of less than 1000 or an alicyclic or aliphatic compound having a carboxylic acid group).

[1025] The resist composition may further include a dissolution-inhibiting compound. Here, "dissolution-inhibiting compound" refers to a compound with a molecular weight of less than 3000 that decomposes under the action of acid and has reduced solubility in organic developers.

[1026] The resist composition of the present invention is suitable for use as a photosensitive composition for EUV light.

[1027] EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm), resulting in fewer incident photons when exposed to the same sensitivity. Therefore, the "photon shot noise," caused by the random variation in the number of photons, has a significant impact, leading to LER degradation and bridging defects. To reduce photon shot noise, methods exist to increase the number of incident photons by increasing the exposure, but this is a trade-off with the requirement for high sensitivity.

[1028] When the value of A, calculated by the following formula (1), is high, the absorption efficiency of EUV light and electron beam in the resist film formed by the resist composition becomes higher, which is effective in reducing photon shot noise. The value of A represents the absorption efficiency of EUV light and electron beam in the mass ratio of the resist film.

[1029] Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127)

[1030] The A value is preferably 0.120 or higher. There is no particular upper limit, but when the A value is too large, the EUV light and electron beam transmittance of the resist film decreases, the optical image contour in the resist film deteriorates, and it is difficult to obtain a good pattern shape. Therefore, it is preferably 0.240 or lower, and more preferably 0.220 or lower.

[1031] In addition, in formula (1), [H] represents the molar ratio of hydrogen atoms from the total solids component to all atoms of the total solids component in the photosensitive radioactive or radioactive linear resin composition, [C] represents the molar ratio of carbon atoms from the total solids component to all atoms of the total solids component in the photosensitive radioactive or radioactive linear resin composition, [N] represents the molar ratio of nitrogen atoms from the total solids component to all atoms of the total solids component in the photosensitive radioactive or radioactive linear resin composition, [O] represents the molar ratio of oxygen atoms from the total solids component to all atoms of the total solids component in the photosensitive radioactive or radioactive linear resin composition, [F] represents the molar ratio of fluorine atoms from the total solids component to all atoms of the total solids component in the photosensitive radioactive or radioactive linear resin composition, [S] represents the molar ratio of sulfur atoms from the total solids component to all atoms of the total solids component in the photosensitive radioactive or radioactive linear resin composition, and [I] represents the molar ratio of iodine atoms from the total solids component to all atoms of the total solids component in the photosensitive radioactive or radioactive linear resin composition.

[1032] For example, when the resist composition contains a resin whose polarity increases through the action of acid (acid-degrading resin), a photoacid generator, an acid diffusion control agent, and a solvent, the resin, the photoacid generator, and the acid diffusion control agent are equivalent to the solid components. That is, all atoms of the total solid components are equivalent to the total number of atoms derived from the resin, the photoacid generator, and the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid components to all atoms of the total solid components. Based on the above example, [H] represents the molar ratio of the total number of hydrogen atoms derived from the resin, the photoacid generator, and the acid diffusion control agent to the total number of atoms derived from the resin, the photoacid generator, and the acid diffusion control agent.

[1033] The A value can be calculated by determining the structure of the constituent components of the total solids in the resist composition and the atomic ratio when the content is known. Furthermore, even when the constituent components are unknown, the atomic ratio can be calculated using analytical methods such as elemental analysis for the resist film obtained by evaporating the solvent components of the resist composition.

[1034] [Resist film and pattern formation method]

[1035] There are no particular limitations on the steps of the pattern forming method using the above-described resist composition, but the following steps are preferred.

[1036] Step 1: A step of forming a resist film on a substrate using a resist composition.

[1037] Step 2: The process of exposing the resist film.

[1038] Step 3: The process of developing the exposed resist film with a developing solution to form a pattern.

[1039] The steps of each of the above processes will be explained in detail below.

[1040] <Process 1: Resist Film Formation Process>

[1041] Step 1 is a step of forming a resist film on a substrate using a resist composition.

[1042] The definition of the resist composition is as described above.

[1043] As a method for forming a resist film on a substrate using a resist composition, one example is the method of coating the resist composition onto the substrate.

[1044] Furthermore, it is preferable to filter the resist composition as needed before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[1045] The photoresist composition can be applied to substrates (e.g., silicon, silicon dioxide coatings) used in the manufacture of integrated circuit components using a suitable coating method such as a spin coater or a coating machine. Spin coating using a spin coater is preferred. The rotation speed when performing spin coating using a spin coater is preferably 1000–3000 rpm.

[1046] A resist film can be formed by drying the substrate after coating the resist composition. Additionally, various substrate films (inorganic films, organic films, and anti-reflective films) can be formed under the resist film as needed.

[1047] As a drying method, drying by heating can be cited as an example. Heating can be carried out using devices found in general exposure machines and / or developing machines, or by using hot plates or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[1048] There is no particular limitation on the thickness of the resist film, but from the viewpoint of being able to form finer patterns with higher precision, it is preferably 10 to 65 nm, and more preferably 15 to 50 nm.

[1049] Alternatively, a topcoat composition can be used to form a topcoat layer on top of the resist film.

[1050] The preferred topcoat composition can be applied more evenly to the top layer of the resist film without mixing with it.

[1051] There are no particular limitations on the top coating. A conventionally known top coating can be formed by conventionally known methods. For example, the top coating can be formed based on the content described in paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543.

[1052] For example, it is preferable to form a top coating containing an alkaline compound, such as that described in Japanese Patent Application Publication No. 2013-61648, on the resist film. Specific examples of alkaline compounds that the top coating may contain include alkaline compounds that the resist composition may contain.

[1053] Furthermore, the top coating preferably contains a compound that includes at least one group or bond selected from ether bonds, thioether bonds, hydroxyl groups, thiols, carbonyl bonds, and ester bonds.

[1054] <Process 2: Exposure Process>

[1055] Step 2 is the process of exposing the resist film.

[1056] As an example of exposure method, one could irradiate the formed resist film with EUV light through a prescribed mask.

[1057] It is preferable to bake (heat) the exposed area after exposure and before development. Baking promotes the reaction of the exposed part, and the sensitivity and pattern shape become better.

[1058] The heating temperature is preferably 80-150°C, more preferably 80-140°C, and even more preferably 80-130°C.

[1059] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.

[1060] Heating can be achieved using devices found in general exposure machines and / or developing machines, or by using hot plates or the like.

[1061] This process is also known as post-exposure baking.

[1062] <Step 3: Development Step>

[1063] Step 3 is the process of developing the exposed resist film with a developing solution to form a pattern.

[1064] The developer can be an alkaline developer or a developer containing organic solvents (hereinafter also referred to as "organic developer").

[1065] Examples of development methods include: immersing the substrate in a tank filled with developer for a certain time (dip method); developing the substrate by causing the developer to bulge on the substrate surface through surface tension and then allowing it to stand for a certain time (puddle method); spraying developer onto the substrate surface (spray method); and continuously dispensing developer onto a substrate rotating at a certain speed while scanning the developer nozzle at a certain speed (dynamic dispense method).

[1066] Furthermore, after the developing process, a process can be implemented where the developing process is stopped while the solvent is being replaced with another solvent.

[1067] There are no particular limitations as long as the development time is the time it takes for the resin in the unexposed area to fully dissolve; preferably, it is 10 to 300 seconds, and more preferably 20 to 120 seconds.

[1068] The temperature of the developer is preferably 0–50°C, and more preferably 15–35°C.

[1069] Alkaline developers preferably use aqueous solutions containing alkali. There are no particular limitations on the type of alkaline solution; examples include aqueous solutions containing quaternary ammonium salts (e.g., tetramethylammonium hydroxide), inorganic bases, primary amines, secondary amines, tertiary amines, alkanolamines, or cyclic amines. Among these, aqueous solutions containing quaternary ammonium salts, such as tetramethylammonium hydroxide (TMAH), are preferred. Appropriate amounts of alcohols and surfactants may be added to the alkaline developer. The alkali concentration of the alkaline developer is typically 0.1–20% by mass. Furthermore, the pH of the alkaline developer is typically 10.0–15.0.

[1070] Organic developer solutions are preferably developer solutions containing at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents.

[1071] <Other processes>

[1072] The above pattern forming method preferably includes a cleaning step using a rinsing solution after step 3.

[1073] As a rinsing solution used in the rinsing process following the development process using an alkaline developer, pure water can be an example. Additionally, an appropriate amount of surfactant can be added to the pure water.

[1074] An appropriate amount of surfactant can be added to the rinsing solution.

[1075] In the rinsing process following the developing step using an organic developer, there are no particular restrictions on the rinsing solution used, as long as it does not dissolve the pattern; solutions containing common organic solvents can be used. Preferably, the rinsing solution contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[1076] Examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include solvents that are the same as those described in the developing solution containing organic solvents.

[1077] There are no particular limitations on the rinsing process. For example, methods such as continuously spraying rinsing liquid onto a substrate rotating at a certain speed (spin coating), immersing the substrate in a tank filled with rinsing liquid for a certain time (immersion method), and spraying rinsing liquid onto the substrate surface (spraying method) can be used.

[1078] Furthermore, the pattern forming method of the present invention may include a post-bake step after the rinsing step. This step removes the developer and rinsing solution remaining between and inside the pattern after baking. This step also smooths the resist pattern and improves the surface roughness of the pattern. The post-rinsing step is typically performed at 40–250°C (preferably 90–200°C) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[1079] Furthermore, the formed pattern can be used as a mask to perform etching on the substrate. That is, the pattern formed in step 3 can also be used as a mask to form a pattern on the substrate by processing the substrate (or the lower film and the substrate).

[1080] The processing method of the substrate (or the lower film and substrate) is not particularly limited. Preferred method is to form a pattern on the substrate by using the pattern formed in step 3 as a mask and performing dry etching on the substrate (or the lower film and substrate).

[1081] Dry etching can be a single-stage etching process or an etching process consisting of multiple stages. When etching consists of multiple stages, the etching processes in each stage can be the same or different.

[1082] Etching can be performed using any known method, with various conditions appropriately determined according to the type or application of the substrate. For example, etching can also be performed according to the minutes of the International Society for Optical Engineering (SPIE) Proc. 6924, 692420 (2008) and Japanese Patent Application Publication No. 2009-267112. Furthermore, the method described in Chapter 4, Etching, of the "Semiconductor Process Textbook 4th Edition, 2007, Publisher: SEMI Japan" can also be used.

[1083] Dry etching is preferably oxygen plasma etching.

[1084] The various materials used in the resist composition and the pattern forming method of the present invention (e.g., solvents, developers, rinsing solutions, antireflective film forming compositions, topcoat forming compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 10 ppb by mass or less, further preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably 1 ppt by mass or less. Examples of metallic impurities include, for instance, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[1085] As a method for removing impurities such as metals from various materials, filtration using a filter can be cited as an example. Details of filtration using a filter are described in paragraph

[0321] of International Publication No. 2020 / 004306.

[1086] Furthermore, as methods to reduce impurities such as metals contained in various materials, examples include selecting raw materials with low metal content as the constituent materials, filtering the raw materials that constitute the various materials, and distilling under conditions that suppress contamination as much as possible by lining the device with Teflon (registered trademark).

[1087] Besides filtration, impurities can be removed by adsorption materials, and filtration and adsorption materials can be used in combination. Known adsorption materials can be used, such as inorganic adsorption materials like silica gel and zeolite, and organic adsorption materials like activated carbon. To reduce impurities such as metals contained in these materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been adequately removed from the manufacturing apparatus can be confirmed by measuring the metal content in the cleaning solution used during cleaning of the manufacturing apparatus. The metal content in the used cleaning solution is preferably 100 parts per trillion (ppt), more preferably 10 ppt, and even more preferably 1 ppt.

[1088] To prevent malfunctions in the chemical solution piping and various components (filters, O-rings, hoses, etc.) caused by static electricity and subsequent electrostatic discharge, a conductive compound can be added to organic processing solutions such as rinsing solutions. There are no particular limitations on the conductive compound; methanol is an example. The amount added is not particularly limited, but from the viewpoint of maintaining preferred developing or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less.

[1089] For pharmaceutical piping, various pipes coated with antistatic-treated polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can be used. Similarly, filters and O-rings can also be made of antistatic-treated polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins).

[1090] The method for improving the surface roughness of a pattern formed by the method of the present invention can also be applied. For example, the method disclosed in International Patent Publication No. 2014 / 002808, which involves processing the pattern with plasma containing hydrogen gas, can be cited. In addition, known methods described in Japanese Patent Application Publication No. 2004-235468, U.S. Patent Application Publication No. 2010 / 0020297, Japanese Patent Application Publication No. 2008-83384, and Proc. of SPIE Vol. 832883280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” can also be cited.

[1091] When the formed pattern is linear, the aspect ratio obtained by dividing the pattern height by the line width is preferably 2.5 or less, more preferably 2.1 or less, and even more preferably 1.7 or less.

[1092] When the formed pattern is a groove pattern or a contact hole pattern, the aspect ratio obtained by dividing the pattern height by the groove width or hole diameter is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.

[1093] The patterning method of the present invention can also be used for guided patterning in DSA (Directed Self-Assembly) (e.g., see ACS Nano Vol.4 No.84815-4823).

[1094] Furthermore, the pattern formed by the above method can be used as the core material in the spacer process disclosed in, for example, Japanese Patent Application Publication No. 3-270227 and Japanese Patent Application Publication No. 2013-164509.

[1095] [Methods for manufacturing specific compounds]

[1096] There are no particular limitations on the method of manufacturing a specific compound, but the following method is preferred: it has a step of reacting a compound having at least one cation represented by general formula (4) with a compound represented by general formula (5) in the presence of an alkaline compound to manufacture the specific compound.

[1097] The following sections will first describe in detail the materials used in the above manufacturing method, and then describe in detail the steps of the manufacturing method.

[1098] <Compounds having cations represented by general formula (4)>

[1099] In a method for manufacturing a particular compound, a compound having at least one cation represented by general formula (4) is used.

[1100] [Chemical Formula 75]

[1101] (R d1 ) m -[X d1 ] + -(L d1 -Ar d1 -(R d3 ) p ) n (4)

[1103] In general formula (4), Xd1 R d1 L d1 Ar d1 The definitions of , n, m and p are respectively the same as X in the above general formula (1). d1 R d1 L d 1. Ar d1 The definitions of , n, m and p are the same.

[1104] R d3 This represents a halogen atom.

[1105] As a result of R d3 The halogen atom represented can be, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of superior performance of the present invention, R... d3 The preferred atom is fluorine.

[1106] As a compound having at least one cation represented by general formula (4), it is preferably a compound represented by general formula (4-1) or a compound represented by general formula (4-2).

[1107] General formula (4-1)Z p + Y1 -

[1108] In general formula (4-1), Z p + This represents the cation represented by general formula (4).

[1109] Y1 - This refers to organic anions with a monovalent valence. An organic anion with a monovalent valence refers to the organic anion with a monovalent valence among the aforementioned organic anions.

[1110] [Chemical Formula 76]

[1111]

[1112] In general formula (4-2), Z p + Z represents a cation. p + At least one of them represents a cation represented by general formula (4). There are no particular limitations on cations other than those represented by general formula (4), and well-known examples include sulfonium cations and iodonium cations.

[1113] Y2 - This indicates anionic functional groups. The definition of anionic functional groups is as described above.

[1114] L represents the linking basis with q valence. q represents an integer greater than 2. The definitions of L and q are the same as those in general formula (3).

[1115] The compound represented by general formula (4) is preferably the compound represented by general formula (U-1).

[1116] [Chemical Formula 77]

[1117]

[1118] In general formula (U-1), Y1 - This refers to organic anions with a monovalent valence. An organic anion with a monovalent valence refers to the organic anion with a monovalent valence among the aforementioned organic anions.

[1119] R U1 ~R U3 Each halogen atom is represented independently.

[1120] R U11 ~R U13 Each organic group can be represented independently.

[1121] R U11 ~R U13 R in general formula (S-1) b1 ~R b3 They have the same meaning.

[1122] In general formula (U-1), a1~a3 and b1~b3 have the same meaning as in general formula (S-1).

[1123] <Compounds represented by general formula (5)>

[1124] In the manufacturing method of a particular compound, a compound represented by general formula (5) is used.

[1125] General formula (5) HS-X d2

[1126] In general formula (5), X d2 This indicates a group represented by the general formula (1-1) or a detached group that is released by the action of an acid.

[1127] Equation (1-1)*-L d2 -R d2

[1128] In equation (1-1), L d2 Represents a single bond or a divalent linker. R d2 This indicates a group whose polarity increases due to decomposition by acid. * indicates a bonding position.

[1129] X in general formula (5) d2 And in general formula (1-1), L d2 and R d2 The definition is as described above.

[1130] <Alkaline compounds>

[1131] In the manufacturing process of certain compounds, basic compounds are used.

[1132] As a basic compound, it can also be an organic or inorganic compound.

[1133] Examples of basic compounds include primary amine to quaternary amine compounds, metal salts, and organometallic compounds such as alkoxymetal compounds. Furthermore, basic compounds that function as acid diffusion control agents can also be used. Preferably, the basic compound is a carbonate or hydroxide of an alkali metal or alkaline earth metal.

[1134] Examples of organic compounds include amine compounds such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-(β-aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine, and their derivatives; piperazine compounds such as anhydrous piperazine, piperazine hexahydrate, 1-(2-aminoethyl)piperazine, and N-methylpiperazine, and their derivatives; pyridine compounds such as pyridine, pyrimidine, quinoline, and acridine, and their derivatives; azole compounds such as imidazole and triazole, and their derivatives; ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide, and their derivatives; and guanidine.

[1135] Examples of inorganic compounds include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metal hydrides such as lithium hydride and sodium hydride; and alkaline earth metal hydrides such as magnesium hydride and calcium hydride.

[1136] One basic compound can be used alone, or two or more compounds can be used.

[1137] Solvent

[1138] Solvents may be used in the manufacturing process of certain compounds.

[1139] There are no particular restrictions on the solvent used, as long as it is a solvent that dissolves the material being used. Solvents containing the aforementioned resist composition can also be used as solvents.

[1140] As a solvent, it can be an organic solvent or an aqueous solvent.

[1141] Examples of solvents include alcohol solvents such as methanol and ethanol; alkane solvents such as hexane, cyclohexane, and heptane; ester solvents, ketone solvents such as cyclohexanone and methyl-2-n-pentyl ketone; ether solvents such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and diethylene glycol dimethyl ether; ester solvents such as ethyl acetate, butyl acetate, and acetic acid; and lactone solvents such as γ-butyrolactone.

[1142] Solvent A is preferably an alcohol-based solvent such as methanol or ethanol, and more preferably methanol or ethanol.

[1143] One solvent can be used alone, or two or more solvents can be used.

[1144] <Steps>

[1145] There are no particular restrictions on the steps of the manufacturing method as long as the compound represented by general formula (4) can react with the compound represented by general formula (5) in the presence of an alkaline compound.

[1146] For example, a compound represented by general formula (4) and a compound represented by general formula (5) can be added to a reaction system in the presence of a basic compound and allowed to react.

[1147] The ratio of the amount of compound represented by general formula (5) to the amount of compound represented by general formula (4) (the amount of compound represented by general formula (5) / the amount of compound represented by general formula (4)) is not particularly limited, but from the viewpoint of excellent yield of a particular compound, it is preferably 3.0 to 1.0, more preferably 2.0 to 1.0.

[1148] The ratio of the amount of basic compound used to the amount of compound represented by general formula (5) (amount of basic compound used / amount of compound represented by general formula (5)) is not particularly limited, but from the viewpoint of achieving excellent yield of a particular compound, it is preferably 5.0 to 1.0, and more preferably 3.0 to 1.0.

[1149] There are no particular limitations on the reaction temperature, but it is preferably -50℃ to 100℃, more preferably -30℃ to 50℃, and even more preferably -10℃ to 10℃.

[1150] There is no particular limitation on the reaction time, but it is preferably 1 minute to 24 hours, and more preferably 10 minutes to 1 hour.

[1151] Furthermore, the present invention relates to a method for manufacturing an electronic device including the above-described pattern forming method, and to an electronic device manufactured by the same method.

[1152] The electronic device of the present invention is suitable for mounting on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[1153] Example

[1154] The present invention will now be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the embodiments shown below.

[1155] [Preparation of the photoresist composition (photosensitive radioactive or radiosensitive linear resin composition)]

[1156] The following shows the components and manufacturing steps of the resist compositions used in the examples or comparative examples.

[1157] <Specific compound>

[1158] (Synthesis Example 1: Synthesis of Compound B-1)

[1159] Compound B-1 was synthesized according to the following scheme.

[1160] [Chemical Formula 78]

[1161]

[1162] 25 g of tert-butyl bromoacetate and 125 g of acetone were added to a three-necked flask, followed by 17.5 g of sodium thioacetate. The resulting solution was stirred at room temperature for 2 hours. Then, 100 ml of water and 150 g of ethyl acetate were added to the solution, and the organic phase was separated. The obtained organic phase was washed sequentially with 100 g of water and 100 g of a saturated sodium chloride aqueous solution. Finally, 23 g of the target compound B-1A was obtained by concentrating the organic phase.

[1163] 1 H-NMR, 400MHz, δ (CDCl3) ppm: 1.46 (9H, s), 3.62 (3H, s)

[1164] Compound B-1B was synthesized with reference to the following paper.

[1165] Imazeki, Shigeaki; Sumino, Motoshige; Fukasawa, Kazuhito; Ishihara, Masami; Akiyama, Takahiko [Synthesis, 2004, #10, p.1648-1654

[1166] Compound B-1A (4.0 g), methanol (50 g), and potassium carbonate (12.3 g) were added to a three-necked flask, and the resulting solution was stirred at 0 °C for 30 minutes. Then, 4-fluorophenyldiphenylsulfonium bromide (compound B-1B, 7.6 g) was added to the resulting solution, and the solution was stirred at 0 °C for another 30 minutes. Next, water (100 g) and dichloromethane (150 g) were added to the resulting solution, the organic phase was separated, and the solution was washed sequentially with water (50 g) and a saturated sodium chloride aqueous solution (50 g). The target compound B-1C (9.2 g) was then obtained by concentrating the organic phase. Compound B-1C was used immediately in subsequent processes without further purification.

[1167] Compound B-1C (9.2 g), dichloromethane (50 g), and water (30 g) were added to a three-necked flask, and the resulting solution was stirred at room temperature for 30 minutes. Then, compound B-1D (8.2 g) was added, and the solution was further stirred at 0°C for 30 minutes. The organic phase was then separated, washed with 0.01 N hydrochloric acid water (50 g), and then washed five times with water (30 g). The solid obtained by concentrating the organic phase was then washed with diisopropyl ether (50 g) to obtain the target compound B-1 (13.3 g).

[1168] 1 H-NMR, 400MHz, δ (CDCl3) ppm: 1.40-2.05 (24H, m), 3.72 (2H, s), 4.80 (2H, t), 4.41 (2H, brt), 4.53 (2H, td), 7.1-7.83 (14H, m).

[1169] (Synthesis Example 2: Synthesis of Compound B-12)

[1170] [Chemical Formula 79]

[1171]

[1172] Compound B-12A was synthesized with reference to the following paper.

[1173] Imazeki, Shigeaki; Sumino, Motoshige; Fukasawa, Kazuhito; Ishihara, Masami; Akiyama, Takahiko [Synthesis, 2004, #10, p.1648-1654.

[1174] Compound B-1A (15.3 g) and methanol (50 g) were added to a three-necked flask. After stirring at 0 °C, potassium carbonate (15.0 g) was added to the resulting solution and the mixture was stirred for 30 minutes. Then, tris(4-fluorophenyl)sulfonium bromide (10 g, compound B-12A) was added, and the resulting solution was stirred at 0 °C for another 30 minutes. Water (100 ml) and chloroform (100 ml) were then added to the resulting solution, the organic phase was separated, and the solution was washed with water (100 g). The organic phase was then concentrated to obtain 18.3 g of the target compound B-12B.

[1175] 1 H-NMR, 400MHz, δ (CDCl3) ppm: 1.46 (27H, s), 3.68 (6H, s), 7.52 (6H, d), 7.76 (6H, d).

[1176] Compound B-12B (7.8 g), compound B-12C (3.4 g), chloroform (50 g), and water (30 g) were added to a three-necked flask and stirred at room temperature for 30 minutes. The organic phase was then separated, washed with 0.01 N hydrochloric acid water (30 g), and then washed five times with water (30 g). The solid obtained from concentrating the organic phase was then washed with 50 g of cyclopentyl methyl ether to obtain the target compound B-12 (9.8 g).

[1177] 1 H-NMR, 400MHz, δ (CDCl3) ppm: 1.43 (27H, s), 3.72 (6H, s), 7.48 (6H, d), 7.80 (6H, d).

[1178] (Synthesis Example 3: Synthesis of Compound B-17)

[1179] [Chemical Formula 80]

[1180]

[1181] Compound B-12A (7.5 g), compound B-17A (2.5 g), dichloromethane (100 g), and water (90 g) were added to a three-necked flask and stirred at room temperature for 30 minutes. The organic phase was then separated, washed with 0.01 N hydrochloric acid water (50 g), and then washed five times with water (50 g). The viscous liquid obtained by concentrating the organic phase was then decanted with diisopropyl ether (50 g) to obtain the target compound B-17 (8.7 g).

[1182] 1H-NMR, 400MHz, δ(CDCl3)ppm: 1.43(81H,s), 3.69(18H,s), 6.91(2H,d), 7.49(18H,d), 7.55(18H,d), 7.86(2H,d).

[1183] Other specific compounds were synthesized using the same synthetic methods as those used for the specific compounds B-1, B-12, or B-17 mentioned above.

[1184] The following scheme was used to attempt the synthesis of the comparative compound B-12A', but the intermediate B-12A” could not be isolated and purified, and the comparative compound B-12A' could not be synthesized.

[1185] [Chemical Formula 81]

[1186]

[1187] The following shows specific compounds B-1 to B-26 used in the examples.

[1188] [Chemical Formula 82]

[1189]

[1190] [Chemical Formula 83]

[1191]

[1192] The following shows the comparative compound Z-1.

[1193] [Chemical Formula 84]

[1194]

[1195] <Acid-degradable resin (resin (A))>

[1196] (Synthesis Example 1: Synthesis of Resin A-1)

[1197] Resin A-1 was synthesized according to the following scheme.

[1198] [Chemical Formula 85]

[1199]

[1200] Cyclohexanone (113 g) was heated to 80°C under a nitrogen atmosphere. While stirring the solution, a mixed solution of monomer (25.5 g) represented by formula M-1, monomer (31.6 g) represented by formula M-2, cyclohexanone (210 g), and dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation] (6.21 g) was added dropwise over 6 hours to obtain a reaction solution. After the addition was complete, the reaction solution was further stirred at 80°C for 2 hours. The obtained reaction solution was allowed to cool naturally, then precipitated with a large amount of methanol / water (mass ratio 9:1), filtered, and the obtained solid was dried under vacuum to obtain 52 g of resin A-1.

[1201] Resins A-2 to A-30 were synthesized using the same method as resin A-1 described above.

[1202] Table 1 shows the composition ratio (molar ratio; corresponding from left to right), weight-average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit described later.

[1203] In addition, the weight-average molecular weight (Mw) and dispersity (Mw / Mn) of resins A-1 to A-30 were determined by GPC (charge carrier: tetrahydrofuran (THF)) (converted to polystyrene). Furthermore, through... 13 The composition ratio (molar percentage) of the resin was determined by C-NMR (nuclear magnetic resonance).

[1204] [Table 1]

[1205]

[1206] The following shows resins A-1 to A-30. * indicates the bonding position.

[1207] [Chemical Formula 86]

[1208]

[1209] [Chemical Formula 87]

[1210]

[1211] [Chemical Formula 88]

[1212]

[1213] <Acid diffusion control agent>

[1214] The following shows acid diffusion control agents C-1 to C-9.

[1215] [Chemical Formula 89]

[1216]

[1217] The following are examples of acid diffusion control agents D-1 to D-11, other than those mentioned above.

[1218] [Chemical Formula 90]

[1219]

[1220] <Hydrophobic Resins and Topcoat Resins>

[1221] Hydrophobic resins (E-1 to E-11) and topcoat resins (PT-1 to PT-3) were synthesized according to Table 2.

[1222] Furthermore, the molar ratio, weight-average molecular weight (Mw), and dispersion (Mw / Mn) of the repeating units in the hydrophobic resins (E-1 to E-11) and the topcoat resins (PT-1 to PT-3) are shown in Table 2.

[1223] In addition, the weight-average molecular weight (Mw) and dispersibility (Mw / Mn) of hydrophobic resins E-1 to E-11 or topcoat resins PT-1 to PT-3 were determined by GPC (charge carrier: tetrahydrofuran (THF)) (converted to polystyrene). Furthermore, through... 13 The composition ratio (molar percentage) of the resin was determined by C-NMR (huclear magnetic resonance).

[1224] [Table 2]

[1225]

[1226] The following shows the monomers ME-1 to ME-20 used in the synthesis of hydrophobic resins E-1 to E-11 and topcoat resins PT-1 to PT-3 shown in Table 2.

[1227] [Chemical Formula 91]

[1228]

[1229] <Preparation of Anti-corrosion Composition>

[1230] (Preparation of resist compositions for ArF exposure testing (Re-1 to Re-16))

[1231] The components shown in Table 3 were mixed to achieve a solid component concentration of 4% by mass. The resulting mixture was then filtered first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm, thereby preparing the resist composition. In the resist composition, "solid component" refers to all components except the solvent. The obtained resist composition was used in the examples and comparative examples.

[1232] In addition, in Table 3, the content (mass%) of each component refers to the content relative to the total solids content.

[1233] (Preparation of resist compositions for EUV exposure testing (Re-17~Re-41))

[1234] The components shown in Table 4 were mixed to a solid component concentration of 2% by mass. The resulting mixture was then filtered first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm, thereby preparing the resist composition. In the resist composition, solid component refers to all components except the solvent. The obtained resist composition was used in the examples and comparative examples.

[1235] The following shows the proportions of each resist composition.

[1236] [Table 3]

[1237]

[1238] [Table 4]

[1239]

[1240] <surfactants>

[1241] When the resist composition contains a surfactant, the following surfactant is used.

[1242] H-1: Megaface F176 (manufactured by DIC CORPORATION, a fluorinated surfactant)

[1243] H-2: Megaface R08 (manufactured by DIC CORPORATION, a fluorinated and silicone-based surfactant).

[1244] H-3: PF656 (manufactured by OMNOVA Solutions Inc., a fluorinated surfactant)

[1245] Solvent

[1246] The following shows the solvents contained in the resist composition.

[1247] F-1: Propylene glycol monomethyl ether acetate (PGMEA)

[1248] F-2: Propylene glycol monomethyl ether (PGME)

[1249] F-3: Propylene glycol monoethyl ether (PGEE)

[1250] F-4: Cyclohexanone

[1251] F-5: Cyclopentanone

[1252] F-6: 2-Heptanone

[1253] F-7: Ethyl lactate

[1254] F-8: γ-Butyrolactone

[1255] F-9: Propylene carbonate

[1256] [Preparation of the topcoat composition]

[1257] The following table shows the various components contained in the topcoat composition shown in Table 5.

[1258] <Resin>

[1259] As shown in Table 5, resins PT-1 to PT-3 shown in Table 2 were used.

[1260] <Preparation of Top Coating Composition>

[1261] The components shown in Table 5 were mixed to achieve a solids concentration of 3% by mass. The resulting mixture was then filtered in the following order: first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm, thereby preparing the topcoat composition. Furthermore, the term "solids" here refers to all components except the solvent. The obtained topcoat composition was used in the examples.

[1262] [Table 5]

[1263]

[1264] <Additives>

[1265] The structures of the additives shown in Table 5 are shown below.

[1266] [Chemical Formula 92]

[1267]

[1268] <surfactants>

[1269] The surfactant H-3 mentioned above was used as the surfactant shown in Table 5.

[1270] Solvent

[1271] The solvents shown in Table 5 are listed below.

[1272] FT-1: 4-Methyl-2-pentanol (MIBC)

[1273] FT-2: n-Decane

[1274] FT-3: Diisopentyl ether

[1275] [Pattern formation (1): ArF immersion exposure, organic solvent development]

[1276] An organic antireflective film forming composition ARC29SR (manufactured by Brewer Science) was coated onto a silicon wafer and baked at 205°C for 60 seconds to form an antireflective film with a thickness of 98 nm. A resist composition as shown in Table 3 was then coated onto the wafer (refer to Tables 3 and 4 for the composition of the resist composition), and baked at 100°C for 60 seconds to form a resist film (photosensitive or radiosensitive linear film) with a thickness of 90 nm. Furthermore, in Examples 1-5, 1-6, and 1-12, a topcoat film was formed on top of the resist film. The thickness of the topcoat film was set to 100 nm in all cases.

[1277] For the resist film, an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, Dipole, outer sigma 0.950, inner sigma 0.850, Y-polarized) was used for exposure through a 6% halftone mask with a 1:1 line-space pattern and a linewidth of 45 nm. Ultrapure water was used as the immersion solution.

[1278] After the exposed resist film was baked at 90°C for 60 seconds, it was developed with n-butyl acetate for 30 seconds, followed by rinsing with 4-methyl-2-pentanol for 30 seconds. Then, it was rotated to dry, thus obtaining a negative pattern.

[1279] <Defect Evaluation>

[1280] After forming the aforementioned 45nm linewidth pattern, the defect distribution on the silicon wafer was inspected using a UVision5 (manufactured by AMAT Corporation), and the shape of the defects was observed using a SEMVisionG4 (manufactured by AMAT Corporation). The number of defects per silicon wafer was counted, and the results were evaluated according to the following criteria. The fewer the defects, the better the result. The evaluation results are shown in Table 6 below.

[1281] "A": The number of defects is less than 100

[1282] "B": The number of defects exceeds 100 and is less than or equal to 300

[1283] "C": The number of defects exceeds 300 and is less than or equal to 500

[1284] "D": The number of defects exceeds 500

[1285] <LWR Evaluation>

[1286] For a 45 nm (1:1) line-and-space pattern obtained by analyzing the optimal exposure dose for analyzing a line pattern with an average line width of 45 nm, when observed from above the pattern using a length measurement scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), the line width was observed at any point, and its measurement deviation was evaluated by 3σ. The smaller the value, the better the performance. In addition, LWR (nm) is preferably 2.8 nm or less, more preferably 2.5 nm or less, further preferably 2.3 nm or less, and particularly preferably 2.0 nm or less. The evaluation results are shown in Table 6 below.

[1287] In Table 6, in the "X d2 " column, "A" indicates that X d2 is a group represented by the general formula (1-1), and "B" indicates that X d2 is a dissociable group that dissociates by the action of an acid.

[1288] In Table 6, in the "Acid-decomposable group type", in the case where the "X d2 " column is "A", it indicates which group among the groups represented by the general formulas (a-1) to (a-5) the acid-decomposable group corresponds to. In addition, the notation "(a-1) / (a-1)" indicates that when using two specific compounds, the acid-decomposable groups contained in the specific compounds correspond to any one of the groups.

[1289] In Table 6, the "Number" column indicates the number of acid-decomposable groups or dissociable groups that dissociate by the action of an acid contained in the specific compound.

[1290] [Table 6]

[1291]

[1292] As shown in Table 6, it was confirmed that in the case of performing ArF exposure and obtaining a pattern by developing with an organic solvent, the resist composition of the present invention can form a pattern with excellent LWR performance.

[1293] Among them, it was confirmed by comparison between Examples 1-3, 1-4, 1-7, 1-8 and other examples that more excellent effects can be obtained when the acid-decomposable group is a group represented by the general formula (a-1).

[1294] Moreover, it was confirmed by comparison between Example 1-7 and other examples that more excellent effects can be obtained when the atom represented by X d1 is a sulfur atom.

[1295] Moreover, it was confirmed by comparison with Examples 1-6, 1-10 and 1-14 that more excellent effects can be obtained when the number of acid-decomposable groups and the number of dissociating groups that dissociate by the action of an acid are 2 or more.

[1296] 〔Pattern formation (2): ArF immersion exposure, alkali aqueous solution development〕

[1297] An organic antireflection film-forming composition ARC29SR (manufactured by Brewer Science) was coated on a silicon wafer and baked at 205 °C for 60 seconds to form an antireflection film with a film thickness of 98 nm. The resin composition shown in Table 6 (for the composition of the resin composition, refer to Table 3.) was coated thereon and baked at 100 °C for 60 seconds to form a resist film with a film thickness of 90 nm. In addition, for Examples 2-5 and Example 2-6, a top coat film was formed on the upper layer of the resist film. The film thickness of the top coat film was set to 100 nm in each case.

[1298] Regarding the resist film, an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, Dipole, outer sigma 0.950, inner sigma 0.890, Y deflection) was used, and exposure was performed through a 6% halftone mask of a 1:1 line and space pattern with a line width of 45 nm. Ultrapure water was used as the immersion liquid.

[1299] After baking the exposed resist film at 90 °C for 60 seconds, it was developed with a tetramethylammonium hydroxide aqueous solution (2.38 mass%) for 30 seconds, and then rinsed with pure water for 30 seconds. Thereafter, it was spin-dried to obtain a positive pattern.

[1300] For the obtained positive pattern, the same evaluations as <defect evaluation> and <LWR evaluation> performed in the above-mentioned 〔Pattern formation (1): ArF immersion exposure, organic solvent development〕 were carried out. The evaluation results are shown in Table 7 below.

[1301] In Table 7, in the "X d2 " column, "A" indicates that X d2 is a group represented by the general formula (1-1), and "B" indicates that X d2 is a dissociating group that dissociates by the action of an acid.

[1302] In Table 7, under "Types of Acid-Decomposing Groups", in "X" d2 In the case where the column is marked "A", it indicates which of the groups represented by general formulas (a-1) to (a-5) the acid-degrading group corresponds to. In addition, the notation "(a-1) / (a-1)" indicates that the acid-degrading group contained in the specific compound corresponds to either group when using two specific compounds.

[1303] In Table 7, the "Number" column indicates the number of acid-decomposing groups or detachable groups that are released by the action of acid in a particular compound.

[1304] [Table 7]

[1305]

[1306] As shown in Table 7, it was confirmed that when ArF exposure is performed and the pattern is obtained by developing with an alkaline aqueous solution, the resist composition of the present invention can form a pattern with excellent LWR performance.

[1307] Furthermore, the same trend was observed as in the results of [pattern formation (1): ArF immersion exposure, organic solvent development].

[1308] [Pattern formation (3): EUV exposure, organic solvent development]

[1309] A substrate film with a thickness of 20 nm was formed by coating a silicon wafer with an underlying film forming composition AL412 (manufactured by Brewer Science) and baking it at 205°C for 60 seconds. A resin composition as shown in Table 8 was then coated onto the substrate (refer to Table 4 for the composition of the resin composition), and baked at 100°C for 60 seconds.

[1310] The silicon wafer with the obtained resist film was patterned using an EUV exposure apparatus (manufactured by Exitech Corporation, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). Additionally, a mask with a line size of 20 nm and a line-to-space ratio of 1:1 was used as the reticle.

[1311] After the exposed resist film is baked at 90°C for 60 seconds, it is developed with n-butyl acetate for 30 seconds and then rotated to dry, thus obtaining a negative pattern.

[1312] <Defect Evaluation>

[1313] After forming the pattern with the above line width of 20 nm, the defect distribution on the silicon wafer was then detected using UVision5 (manufactured by AMAT), and the shape of the defects was observed using SEMVisionG4 (manufactured by AMAT). The number of defects on each silicon wafer was counted and evaluated according to the following evaluation criteria. The fewer the number of defects, the better the result. The evaluation results are shown in Table 8 below.

[1314] "A": The number of defects is 100 or less

[1315] "B": The number of defects exceeds 100 and is 300 or less

[1316] "C": The number of defects exceeds 300 and is 500 or less

[1317] "D": The number of defects exceeds 500

[1318] <LWR Evaluation>

[1319] For the 20 nm (1:1) line and space pattern obtained by analyzing the optimal exposure dose for analyzing the line pattern with an average line width of 20 nm, when observed from above the pattern using a length measurement scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), the line width was observed at any point, and its measurement deviation was evaluated by 3σ. The smaller the value, the better the performance. In addition, LWR (nm) is preferably 4.2 nm or less, more preferably 3.8 nm or less, further preferably 3.5 nm or less, particularly preferably 3.2 nm or less, most preferably 3.0 nm or less, and particularly most preferably 2.9 nm or less. The evaluation results are shown in Table 8 below.

[1320] In Table 8, in the "X d2 " column, "A" indicates that X d2 is a group represented by the general formula (1-1), and "B" indicates that X d2 is a dissociable group that dissociates by the action of an acid.

[1321] In Table 8, in the "Acid-Dissociable Group Type", in the case where the "X d2 " column is "A", it indicates which group among the groups represented by the general formulas (a-1) to (a-5) the acid-dissociable group corresponds to. In addition, the notation "(a-1) / (a-1)" indicates that when using two specific compounds, the acid-dissociable group contained in the specific compound corresponds to any one of the groups.

[1322] In Table 8, the "Number" column indicates the number of acid-dissociable groups or dissociable groups that dissociate by the action of an acid contained in the specific compound.

[1323] [Table 8]

[1324]

[1325] As shown in Table 8, it was confirmed that when EUV exposure was carried out and a pattern was obtained by developing with an organic solvent, the resist composition of the present invention was able to form a pattern having excellent LWR performance.

[1326] From the comparison between Examples 3-7, 3-14 and other examples, it was confirmed that in the general formula (1), when X d1 is a sulfur atom, the effect is more excellent.

[1327] From the comparison with Examples 3-3, 3-7, 3-8 and 3-12, it was confirmed that in the general formula (1), when the group whose polarity increases by decomposition by the action of an acid is the group represented by the general formula (a-1), the effect is more excellent.

[1328] From the results in Table 8 above, it was confirmed that when the number of acid-decomposable groups and the number of dissociating groups that dissociate by the action of an acid are 2 or more, more excellent effects can be obtained.

[1329] [Pattern formation (4): EUV exposure, development with an aqueous alkali solution]

[1330] A composition AL412 for forming a lower layer film (manufactured by Brewer Science) was coated on a silicon wafer and baked at 205 °C for 60 seconds, thereby forming a base film with a film thickness of 20 nm. A resin composition shown in Table 9 (for the composition of the resin composition, refer to Table 4.) was coated thereon and baked at 100 °C for 60 seconds, thereby forming a resist film with a film thickness of 30 nm.

[1331] Using an EUV exposure apparatus (manufactured by Exitcch Corporation, Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), pattern irradiation was performed on the silicon wafer having the obtained resist film. In addition, as a reticle, a mask having a line size of 20 nm and a line:space ratio of 1:1 was used.

[1332] After baking the exposed resist film at 90 °C for 60 seconds, it was developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. Thereafter, it was spin-dried to obtain a positive pattern.

[1333] For the obtained positive pattern, the same evaluations as <defect evaluation> and <LWR evaluation> performed in the above [Pattern formation (3): EUV exposure, development with an organic solvent] were carried out. The evaluation results are shown in Table 9 below.

[1334] [Table 9]

[1335]

[1336] As shown in Table 9, it was confirmed that when EUV exposure is performed and the pattern is obtained by developing with an alkaline aqueous solution, the resist composition of the present invention can form a pattern with excellent LWR performance.

[1337] Furthermore, the same trend was observed as in the results of [pattern formation (3): EUV exposure, organic solvent development].

Claims

1. A photosensitive or radiosensitive linear resin composition comprising a resin having repeating units containing groups whose polarity increases upon decomposition by acid action. The photosensitive radioactive or radiosensitive linear resin composition, in addition to the resin, further comprises a compound having at least one cation represented by general formula (1), or In addition to the repeating units, the resin also has repeating units containing cations represented by general formula (1). In general formula (1), X d1 R represents a sulfur atom or an iodine atom. d1 The term represents a linear, branched, or cyclic alkyl group optionally having substituents, a linear, branched, or cyclic alkenyl group optionally having substituents, or an aryl group optionally having substituents, and when m represents 2, the two R groups... d1 They can be arbitrarily bonded together to form a ring, L d1 Ar represents a linker base that is either a single bond or divalent. d1 X represents an aromatic hydrocarbon cyclogroup with optional substituents. d2 This refers to a group represented by the general formula (1-1) or a detachable group that is released by the action of an acid. General Formula (1-1) *-L d2 -R d2 In general formula (1-1), L d2 R represents a linker base that is either a single bond or divalent. d2 This indicates a group whose polarity increases due to acid decomposition; * indicates a bonding position. When X d1 When representing a sulfur atom, n represents an integer from 1 to 3, m represents an integer from 0 to 2, and m+n equals 3. d1 When representing an iodine atom, n represents 1 or 2, m represents 0 or 1, m+n is 2, and p represents an integer from 1 to 5. wherein, In the general formula (1), n ​​represents an integer from 2 to 3 or p represents an integer from 2 to 5.

2. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1, wherein, The photosensitive radioactive or radiosensitive linear resin composition comprises a compound having at least one cation represented by the general formula (1). A compound having at least one cation represented by the general formula (1) comprises at least one selected from compounds represented by the general formula (2) and compounds represented by the general formula (3). General Formula (2) Z1 + Y1 - In general formula (2), Z1 + Y1 represents the cation represented by the general formula (1). - This represents a monovalent organic anion. In general formula (3), Z2 + Z2 represents a cation. + At least one of them represents a cation represented by the general formula (1), Y2 - L represents an anionic functional group, L represents a q-valent linker, and q represents an integer greater than 2.

3. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, X d1 is a sulfur atom.

4. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, In the general formula (1), the group whose polarity increases due to decomposition by the action of acid is the group represented by general formula (a-1). In General Formula (a-1), R a1 represents a leaving group that is detached by the action of an acid, and * represents a bonding position.

5. A resist film formed using any one of the photosensitive radioactive or radiosensitive linear resin compositions according to claims 1 to 4.

6. A method for forming a pattern, comprising the following steps: The process of forming a resist film on a substrate using the photosensitive radioactive or radiosensitive linear resin composition according to any one of claims 1 to 4; The process of exposing the resist film; and The process of developing the exposed resist film with a developer to form a pattern.

7. A method for manufacturing an electronic device, comprising the pattern forming method of claim 6.

8. A compound having at least one cation represented by general formula (1), In general formula (1), X d1 R represents a sulfur atom or an iodine atom. d1 The term represents a linear, branched, or cyclic alkyl group optionally having substituents, a linear, branched, or cyclic alkenyl group optionally having substituents, or an aryl group optionally having substituents, and when m represents 2, the two R groups... d1 They can be arbitrarily bonded together to form a ring, L d1 Ar represents a linker base that is either a single bond or divalent. d1 X represents an aromatic hydrocarbon cyclogroup with optional substituents. d2 This refers to a group represented by general formula (1-1) or a detachable group that is released by the action of an acid. General Formula (1-1) *-L d2 -R d2 In General Formula (1-1), L d2 represents a single bond or a divalent linking group, R d2 represents a group that increases polarity by decomposition by the action of an acid, and * represents a bonding site, When X d1 When representing a sulfur atom, n represents an integer from 1 to 3, m represents an integer from 0 to 2, and m+n equals 3. d1 When representing an iodine atom, n represents 1 or 2, m represents 0 or 1, m+n is 2, and p represents an integer from 1 to 5. wherein In the general formula (1), n ​​represents an integer from 2 to 3 or p represents an integer from 2 to 5.

9. The compound according to claim 8, wherein it is a compound represented by general formula (2) or a compound represented by general formula (3), General Formula (2) Z1 + Y1 - In General Formula (2), Z1 + represents a cation represented by the General Formula (1), Y1 - represents a monovalent organic anion, In general formula (3), Z2 + Z2 represents a cation. + At least one of them represents a cation represented by the general formula (1), Y2 - L represents an anionic functional group, L represents a q-valent linker, and q represents an integer greater than 2.

10. The compound according to claim 8 or 9, wherein, X d1 is a sulfur atom.

11. The compound according to claim 8 or 9, wherein, In the general formula (1), the group whose polarity increases due to decomposition by the action of acid is the group represented by general formula (a-1). In general formula (a-1), R a1 This indicates a detached group that is released by the action of an acid, and * indicates a bonding position.

12. A method for manufacturing a compound, said compound being any one of claims 8 to 11 having at least one cation represented by general formula (1), wherein in the method for manufacturing the compound, In the presence of a basic compound, a compound having at least one cation represented by general formula (4) is reacted with a compound represented by general formula (5) to produce a compound having at least one cation represented by said general formula (1). In general formula (4), X d1 R represents a sulfur atom or an iodine atom. d1 The term represents a linear, branched, or cyclic alkyl group optionally having substituents, a linear, branched, or cyclic alkenyl group optionally having substituents, or an aryl group optionally having substituents, and when m represents 2, the two R groups... d1 They can be arbitrarily bonded together to form a ring, L d1 Ar represents a linker base that is either a single bond or divalent. d1 This indicates an aromatic hydrocarbon cyclic group with optional substituents, where X d1 When representing a sulfur atom, n represents an integer from 1 to 3, m represents an integer from 0 to 2, and m+n equals 3. d1 When representing an iodine atom, n represents 1 or 2, m represents 0 or 1, m+n is 2, p represents an integer from 1 to 5, and R d3 Represents halogen atoms, wherein, In the general formula (4), n represents an integer from 2 to 3 or p represents an integer from 2 to 5. Formula (5) HS-X d2 X d2 represents a group represented by General Formula (1-1) or a leaving group that is detached by the action of an acid, Formula (1-1) *-L d2 -R d2 In equation (1-1), L d2 R represents a linker base that is either a single bond or divalent. d2 This indicates a group whose polarity increases due to decomposition by acid. * indicates the bonding position.

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