Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern formation method, and electronic device manufacturing method

Abstract

The present invention provides: an actinic ray-sensitive or radiation-sensitive resin composition containing a compound (D) represented by general formula (1) described in the specification; an actinic ray-sensitive or radiation-sensitive film using the actinic ray-sensitive or radiation-sensitive resin composition; and an electronic device manufacturing method and a pattern formation method including a step for forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition, a step for exposing the resist film, and a step for developing the exposed resist film using a developer.

Description

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

[0001] The present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device. More specifically, the present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device that can be suitably used in ultra-microlithography processes applicable to processes for manufacturing VLSI (Large Scale Integration) and high-capacity microchips, processes for creating molds for nanoimprinting, and processes for manufacturing high-density information recording media, as well as other photofabrication processes.

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integration), microfabrication is performed by lithography using resist compositions. In recent years, with the increasing integration density of integrated circuits, there has been a demand for ultrafine pattern formation in the submicron or quarter-micron range. Accordingly, there has been a trend toward shorter exposure wavelengths, from g-line to i-line and then to KrF excimer laser light, and currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as a light source have been developed. Furthermore, as a technique for further improving resolution, the so-called immersion method, in which a high refractive index liquid (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample, has been developed.

[0003] Currently, in addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), etc. is also being developed. Accordingly, resist compositions that are effectively sensitive to various types of actinic rays or radiation have been developed.

[0004] Patent Document 1 discloses a resist composition containing an acid generator that is a sulfonate salt having a specific structure containing a pyridine ring.

[0005] Japanese Patent Application Publication No. 2023-21058

[0006] Recently, the performance required of resist compositions has become increasingly higher, and in particular, there is a demand for further improvement in resolution.

[0007] An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

[0008] The present inventors have found that the above problems can be solved by the following configuration.

[0009] [1] An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (D) represented by the following general formula (1):

[0010]

[0011] In general formula (1), Ra represents a nonionic organic group. Rb to Re each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, a halogen atom, a cyano group, an alkoxy group, an alkenyl group, or an alkynyl group. ArN represents a heteroaryl group having a nitrogen atom as a ring member, an aryl group having an amino group as a substituent, or a heteroaryl group having an amino group as a substituent. m and n each independently represent an integer of 0 to 2. L represents a linking group represented by any of the following general formulae (1-1) to (1-7):

[0012]

[0013] In general formulas (1-1) to (1-7), Rf, Rg, Rh, and Ri each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. *1 represents the carbon atom to which Rb is bonded or the bonding site with Ra in general formula (1). *2 represents the carbon atom to which Rd is bonded or the bonding site with ArN in general formula (1).

[0014] [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the formula weight of Ra in the general formula (1) is at least 200. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein Ra in the general formula (1) is an aromatic group.

[0015] [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], which contains a resin (A) that decomposes under the action of an acid to increase its polarity. [5] The actinic ray-sensitive or radiation-sensitive resin composition according to [4], wherein the resin (A) has an aromatic group.

[0016] [6] The actinic ray-sensitive or radiation-sensitive resin composition according to [4] or [5], wherein the resin (A) has a repeating unit represented by the following formula (N-1):

[0017]

[0018] In formula (N-1), R １０１ , R １０２ and R １０３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group, provided that R １０２ is Ar Ａ may be bonded to form a ring, in which case R １０２ represents a single bond or an alkylene group. Ａ represents a single bond or a divalent linking group. Ａ represents an aromatic group; k represents an integer of 0 to 5;

[0019] [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of items [4] to [6], wherein the resin (A) contains at least one selected from the group consisting of a repeating unit represented by the following formula (M-1), a repeating unit represented by the following formula (M-2), and a repeating unit represented by the following formula (M-3):

[0020]

[0021] In formula (M-1), R １１ , R １２ and R １３each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ｍ１ represents a divalent linking group containing an aromatic group. １４ , R １５ and R １６ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. １４ , R １５ and R １６ In formula (M-2), two of R may be bonded to form a ring. ２１ , R ２２ and R ２３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ｍ２ represents a divalent linking group containing an aromatic group. ２４ , R ２５ and R ２６ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ２５ and R ２６ may be bonded to form a ring. Ｍ２ The aromatic group contained in R ２２ or R ２４ In formula (M-3), R ３１ , R ３２ and R ３３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ｍ３ represents a divalent linking group containing an aromatic group. ３４ and R ３５ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３６ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３５ and R ３６ may be bonded to form a ring.

[0022] [8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], further comprising a compound (B) that generates an acid upon irradiation with actinic rays or radiation. [9] The actinic ray-sensitive or radiation-sensitive resin composition according to [8], wherein the compound (B) has a group that decomposes under the action of an acid.

[0023]

[10] The actinic ray-sensitive or radiation-sensitive resin composition according to [8] or [9], wherein the compound (B) is represented by the following formula (U-1):

[0024]

[0025] In formula (U-1), L Ｕ１ represents a single bond or a divalent linking group. Ｕ１ If there are multiple L Ｕ１ may be the same or different. Ｕ１ represents a group that decomposes under the action of an acid. Ｕ１ If there are multiple A's, Ｕ１ may be the same or different. g represents an integer of 1 to 5. X Ｕ１ represents a g+1 valent linking group. Ｕ１ ＋ represents a sulfonium ion or an iodonium ion.

[0026]

[11] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [8] to

[10] , wherein the compound (B) is represented by the following formula (U-2):

[0027]

[0028] In formula (U-2), L Ｕ１ represents a single bond or a divalent linking group. Ｕ１ If there are multiple L Ｕ１ may be the same or different. Ｕ１ represents a group that decomposes under the action of an acid. Ｕ１ If there are multiple A's, Ｕ１ may be the same or different. Ｕ１ represents a substituent. Ｕ１ If there are multiple R Ｕ１may be the same or different. Ｕ１ If there are multiple R Ｕ１ may be bonded to form a ring. g1 represents an integer of 1 to 5. g2 represents an integer of 0 to 4. M Ｕ１ ＋ represents a sulfonium ion or an iodonium ion.

[0029]

[12] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] .

[13] A pattern forming method comprising the steps of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] , exposing the resist film to light, and developing the exposed resist film using a developer.

[14] A method for producing an electronic device, comprising the pattern forming method according to

[13] .

[0030] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution. The present invention can also provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

[0031] The present invention will be described in detail below. The following description of the components will be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0032] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" refers to actinic rays or radiation. Unless otherwise specified, in this specification, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also drawing using particle beams such as electron beams and ion beams. In this specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits.

[0033] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate, and (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0034] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) using a GPC apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0035] In the description of groups (atomic groups) in this specification, unless contrary to the spirit of the present invention, notations that do not specify whether they are substituted or unsubstituted include groups that contain a substituent as well as groups that do not have a substituent. For example, the term "alkyl group" includes not only alkyl groups that do not have a substituent (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group containing at least one carbon atom. Unless otherwise specified, a monovalent substituent is preferred as the substituent. Examples of the substituent include monovalent non-metallic atomic groups excluding hydrogen atoms, which can be selected, for example, from the following substituents T:

[0036] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, Examples of the substituent T include acyl groups such as acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; etc. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0037] In this specification, the bonding direction of a divalent group is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. The compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0038] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation using the following software package 1 based on a database of Hammett's substituent constants and known literature values. All pKa values ​​described in this specification are values ​​determined by calculation using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0039] The pKa can also be calculated by molecular orbital calculation. A specific method for this is to calculate the pKa of H in an aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate the dissociation free energy. ＋ The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, and Gaussian 16 is an example.

[0040] In this specification, pKa refers to a value calculated based on a database of Hammett's substituent constants and publicly known literature values ​​using software package 1, as described above, but if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be adopted.

[0041] In this specification, the term "solid content" refers to components that form an actinic ray-sensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component that forms an actinic ray-sensitive or radiation-sensitive film is considered to be a solid content even if it is in a liquid state.

[0042] [Actinic ray-sensitive or radiation-sensitive resin composition] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") contains a compound (D) represented by the following general formula (1).

[0043]

[0044] In general formula (1), Ra represents a nonionic organic group. Rb to Re each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, a halogen atom, a cyano group, an alkoxy group, an alkenyl group, or an alkynyl group. ArN represents a heteroaryl group having a nitrogen atom as a ring member, an aryl group having an amino group as a substituent, or a heteroaryl group having an amino group as a substituent. m and n each independently represent an integer of 0 to 2. L represents a linking group represented by any of the following general formulae (1-1) to (1-7):

[0045]

[0046] In general formulas (1-1) to (1-7), Rf, Rg, Rh, and Ri each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. *1 represents the carbon atom to which Rb is bonded or the bonding site with Ra in general formula (1). *2 represents the carbon atom to which Rd is bonded or the bonding site with ArN in general formula (1).

[0047] The composition of the present invention is typically a resist composition and may be a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention may be a chemically amplified resist composition or a non-chemically amplified resist composition. An actinic ray-sensitive or radiation-sensitive film can be formed using the composition of the present invention. The actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is preferably a resist film.

[0048] The reason why the resist composition of the present invention has excellent resolution is not clear in detail, but the present inventors speculate as follows. However, the present invention is not limited in any way by the speculated mechanism below. Compound (D) contained in the composition of the present invention has a specific aromatic group containing a nitrogen atom and a specific linking group. The specific aromatic group containing a nitrogen atom is moderately basic, making it difficult to form hydrogen bonds or the like in the resist film, and therefore difficult to form aggregate structures in the resist film. Similarly, the nonionic nature of (D) can also suppress the formation of aggregate structures. In addition, the specific linking group has moderate hydrophilicity and therefore affinity for both alkaline developers and organic solvents. It is believed that these properties contribute to the improved resolution of the composition of the present invention containing compound (D).

[0049] First, the various components of the composition of the present invention will be described in detail below.

[0050] [Compound (D)] The composition of the present invention contains compound (D) represented by the above general formula (1). Compound (D) traps the acid generated from a photoacid generator or the like upon exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in unexposed areas due to excess generated acid.

[0051] In general formula (1), Ra represents a nonionic organic group. The nonionic organic group represented by Ra is not particularly limited, but is preferably an organic group having 1 to 100 carbon atoms, and more preferably an organic group having 5 to 50 carbon atoms.

[0052] Ra may be an aliphatic group or an aromatic group, but preferably contains a hydrocarbon group, and preferably contains at least one of an aliphatic hydrocarbon group (preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms) and an aromatic hydrocarbon group (preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms). The aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be chain-like (straight-chain or branched-chain) or cyclic (alicyclic hydrocarbon group). The aliphatic hydrocarbon group may also contain a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.). When the aliphatic hydrocarbon group contains an oxygen atom, for example, the chain of the chain-like aliphatic hydrocarbon group may contain -O- or -C(=O)O- in the chain or at the end, or the ring of the cyclic aliphatic hydrocarbon group may contain -O- or -C(=O)O- in the ring. The hydrocarbon group may further have a substituent, for example, the above-mentioned substituent T (excluding ionic groups) may be mentioned.

[0053] Ra is -NR Ｑ１ -, -O-, -S-, -C(=O)-, -C(=O)O-, -S(=O)-, and -S(=O) ２ - may contain at least one selected from the group consisting of Ｑ１ represents a hydrogen atom, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms), a cycloalkyl group (for example, a cycloalkyl group having 3 to 20 carbon atoms), or an aryl group (for example, an aryl group having 6 to 20 carbon atoms).

[0054] Ra is preferably an aromatic group, more preferably an aryl group or arylcarbonyl group which may have a substituent, and further preferably a phenyl group or benzoyl group which may have a substituent.

[0055] Ra is preferably a group containing no fluorine atoms, and more preferably a group containing no halogen atoms.

[0056] Ra is preferably a group having a formula weight of 150 or more, more preferably a group having 200 or more, and particularly preferably a group having 250 or more. When the formula weight of Ra is 150 or more, volatilization of compound (D) from the surface of the resist film is suppressed. The upper limit of the formula weight of Ra is preferably, for example, 1000 or less, from the viewpoint of dissolution in a developer, etc.

[0057] In general formula (1), Rb to Re each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, a halogen atom, a cyano group, an alkoxy group, an alkenyl group, or an alkynyl group.

[0058] The alkyl groups represented by Rb to Re may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10.

[0059] The cycloalkyl groups represented by Rb to Re may be monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecanyl groups, tetracyclododecanyl groups, adamantyl groups, etc. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15.

[0060] The aryl group represented by Rb to Re is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably a phenyl group.

[0061] The heteroaryl groups represented by Rb to Re are preferably aromatic groups containing at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms as a ring member. The number of ring atoms in the heteroaryl group is preferably 3 to 20, and more preferably 4 to 15. The number of carbon atoms in the heteroaryl group is preferably 1 to 19, and more preferably 3 to 14.

[0062] Examples of the halogen atoms represented by Rb to Re include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0063] Examples of the alkyl group in the alkoxy group represented by Rb to Re include the alkyl groups described above as Rb to Re, and preferred examples are also the same.

[0064] The alkenyl groups represented by Rb to Re may be linear or branched, and are preferably alkenyl groups having 2 to 20 carbon atoms, and more preferably alkenyl groups having 2 to 15 carbon atoms. Examples of the alkenyl group include a vinyl group and an allyl group.

[0065] The alkynyl groups represented by Rb to Re may be linear or branched, and are preferably alkynyl groups having 2 to 20 carbon atoms, and more preferably alkynyl groups having 2 to 15 carbon atoms. Examples of the alkynyl group include an ethynyl group and a propargyl group.

[0066] Rb to Re may have a substituent.

[0067] Rb to Re preferably represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, more preferably a hydrogen atom, a cyclohexyl group, or a phenyl group, and even more preferably a hydrogen atom.

[0068] In general formula (1), ArN represents a heteroaryl group having a nitrogen atom as a ring member, an aryl group having an amino group as a substituent, or a heteroaryl group having an amino group as a substituent.

[0069] The heteroaryl group represented by ArN and having a nitrogen atom as a ring member may be monocyclic or polycyclic. The number of ring atoms in the heteroaryl group is preferably 3 to 20, and more preferably 4 to 15. The number of carbon atoms in the heteroaryl group is preferably 1 to 19, and more preferably 3 to 14. The number of nitrogen atoms contained as a ring member in the heteroaryl group may be one or two or more. Furthermore, a heteroatom other than a nitrogen atom may be contained.

[0070] The heteroaryl group having a monocyclic nitrogen atom as a ring member is preferably a 5- or 6-membered heteroaryl group, and examples thereof include groups in which one hydrogen atom has been removed from an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, etc. The heteroaryl group having a polycyclic nitrogen atom as a ring member is, for example, a group in which one hydrogen atom has been removed from an indole ring, an isoindole ring, a benzimidazole ring, a purine ring, a benzotriazole ring, a quinoline ring, an isoquinoline ring, an acridine ring, etc.

[0071] Among the heteroaryl groups represented by ArN and having a nitrogen atom as a ring member, groups in which any one hydrogen atom has been removed from a pyridine ring are particularly preferred.

[0072] The aryl group in the aryl group represented by ArN having an amino group as a substituent is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably a phenyl group or a naphthyl group. The number of amino groups in the aryl group is preferably one or two, more preferably one. The amino group is -NH ２ Represents.

[0073] The heteroaryl group in the heteroaryl group represented by ArN having an amino group as a substituent is preferably an aromatic group containing at least one heteroatom selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom as a ring member. The number of ring atoms in the heteroaryl group is preferably 3 to 20, and more preferably 4 to 15. The number of carbon atoms in the heteroaryl group is preferably 1 to 19, and more preferably 3 to 14. The number of amino groups in the heteroaryl group is preferably 1 or 2, and more preferably 1.

[0074] The group represented by ArN may further have a substituent. Examples of the substituent include an alkyl group and an aryl group. When a plurality of substituents are present, the substituents may be bonded to each other to form a ring. In addition, the substituent and the above-mentioned amino group may be bonded to form a ring, or the substituent and the above-mentioned Re may be bonded to form a ring.

[0075] The group represented by ArN is preferably a heteroaryl group having a nitrogen atom as a ring member or an aryl group having an amino group as a substituent, and more preferably a group in which one arbitrary hydrogen atom has been removed from a pyridine ring, a phenyl group having one amino group, or a naphthyl group having one amino group.

[0076] In the general formula (1), m and n each independently represent an integer of 0 to 2. It is preferable that at least one of m and n is an integer of 1 or more.

[0077] In general formula (1), L represents a linking group represented by any one of the above general formulae (1-1) to (1-7). In general formulae (1-1) to (1-7), Rf, Rg, Rh, and Ri each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

[0078] The alkyl groups represented by Rf, Rg, Rh, and Ri may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10. The cycloalkyl groups represented by Rf, Rg, Rh, and Ri may be monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The aryl groups represented by Rf, Rg, Rh, and Ri are preferably aryl groups having 6 to 20 carbon atoms, more preferably aryl groups having 6 to 15 carbon atoms, and even more preferably phenyl or naphthyl groups.

[0079] Rf, Rg, Rh, and Ri preferably represent a hydrogen atom.

[0080] In particular, when L is a linking group represented by any one of (1-1) to (1-5), Ra is an aromatic group, and at least one of m and n is preferably an integer of 1 or more.

[0081] The compound (D) is preferably a compound having no fluorine atom, and more preferably a compound having no halogen atom. If the compound (D) has a halogen atom, particularly a fluorine atom, the surface free energy of the compound is reduced, which leads to deterioration of compatibility with resins in the film, uneven distribution of the compound (D) on the surface, and evaporation of the compound (D) from the film surface, which may result in deterioration of resolution.

[0082] Specific examples of the compound (D) are shown below, but the present invention is not limited to these.

[0083]

[0084]

[0085]

[0086] The content of compound (D) is preferably 0.1 to 30.0 mass%, more preferably 0.5 to 20.0 mass%, and particularly preferably 0.5 to 15.0 mass%, based on the total solid content of the composition of the present invention. Compound (D) may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0087] [Resin (A)] The composition of the present invention contains a resin (A) that decomposes under the action of an acid and increases in polarity. The resin (A) is an acid-decomposable resin, and typically, the polarity of the resin (A) increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent. Furthermore, in a pattern formation method using the composition 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.

[0088] (Repeating unit having an acid-decomposable group) The resin (A) preferably contains a repeating unit having an acid-decomposable group. The acid-decomposable group is preferably a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected with a group that leaves under the action of an acid (leaving group).

[0089] The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as alcoholic hydroxyl groups.

[0090] Examples of the leaving group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1): —C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (R ３７ ) (OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0091] In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Rx each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), an alkenyl group (linear or branched), or an alkynyl group (linear or branched). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched),１ ~Rx ３ At least two of Rx are preferably methyl groups. １ ~Rx ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to each other to form a ring (which may be either a monocyclic or polycyclic ring). １ ~Rx ３ The alkyl group of Rx is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group, and more preferably an alkyl group having 1 to 5 carbon atoms. １ ~Rx ３ The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, more preferably 4 to 15. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. In the cycloalkyl group, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. That is, Rx １ ~Rx ３ may be a cycloalkenylene group. １ ~Rx ３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The aralkyl group of Rx １ ~Rx ３A group in which one hydrogen atom in the alkyl group is substituted with an aryl group (preferably a phenyl group) having 6 to 10 carbon atoms is preferred, and examples thereof include a benzyl group. １ ~Rx ３ Examples of the alkenyl group include alkenyl groups having 2 to 20 carbon atoms, and alkenyl groups having 2 to 10 carbon atoms are preferred, such as vinyl and allyl groups. １ ~Rx ３ Examples of the alkynyl group include alkynyl groups having 2 to 20 carbon atoms, preferably alkynyl groups having 2 to 10 carbon atoms, and for example, an ethynyl group is preferred. １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by combining the two is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. １ ~Rx ３ In the cycloalkyl group formed by bonding these two, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The group represented by formula (Y1) or formula (Y2) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0092] In formula (Y3), R ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. ３６ is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. For example, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have one or more methylene groups replaced with a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. In addition, R ３８ may bond with another substituent on the main chain of the repeating unit to form a ring. ３８ The group formed by bonding together the repeating unit and another substituent carried by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0093] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0094] The resin (A) preferably contains at least one selected from the group consisting of a repeating unit represented by the following formula (M-1), a repeating unit represented by the following formula (M-2), and a repeating unit represented by the following formula (M-3). The repeating unit represented by the following formula (M-1), a repeating unit represented by the following formula (M-2), and a repeating unit represented by the following formula (M-3) are repeating units having an acid-decomposable group. A repeating unit selected from the group consisting of a repeating unit represented by the following formula (M-1), a repeating unit represented by the following formula (M-2), and a repeating unit represented by the following formula (M-3) is also referred to as a "repeating unit (M)."

[0095]

[0096] In formula (M-1), R １１ , R １２ and R １３each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ｍ１ represents a divalent linking group containing an aromatic group. １４ , R １５ and R １６ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. １４ , R １５ and R １６ In formula (M-2), two of R may be bonded to form a ring. ２１ , R ２２ and R ２３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ｍ２ represents a divalent linking group containing an aromatic group. ２４ , R ２５ and R ２６ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ２５ and R ２６ may be bonded to form a ring. Ｍ２ The aromatic group contained in R ２２ or R ２４ In formula (M-3), R ３１ , R ３２ and R ３３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ｍ３ represents a divalent linking group containing an aromatic group. ３４ and R ３５ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３６ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３５ and R ３６ may be bonded to form a ring.

[0097] The repeating unit represented by the above formula (M-1) will be explained. １１ , R１２ and R １３ The alkyl group represented by R may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. １１ , R １２ and R １３ The cycloalkyl group represented by the formula (I) may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or may be a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. In the cycloalkyl group, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. １１ , R １２ and R １３ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. １１ , R １２ and R １３ The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0098] L Ｍ１ represents a divalent linking group containing an aromatic group. Ｍ１ The aromatic group contained in may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Ｍ１ The aromatic group contained in is preferably a divalent group.

[0099] L Ｍ１When the aromatic group contained in is an aromatic hydrocarbon group, the aromatic hydrocarbon group may be either monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 14. The aromatic hydrocarbon group is preferably a phenylene group or a naphthylene group, and more preferably a phenylene group. The aromatic hydrocarbon group may also be a group obtained by removing two hydrogen atoms from a fused ring compound having a structure in which an aromatic hydrocarbon (e.g., benzene, naphthalene, etc.) is condensed with a cycloalkane (e.g., cyclopentane, cyclohexane, etc.).

[0100] L Ｍ１When the aromatic group contained in is an aromatic heterocyclic group, the aromatic heterocyclic group may be either monocyclic or polycyclic. The aromatic heterocyclic group preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but for example, 2 to 18 is preferred, 3 to 15 is more preferred, and 4 to 12 is even more preferred. The number of ring atoms in the aromatic heterocyclic group is not particularly limited, but for example, 5 to 20 is preferred, and 6 to 15 is more preferred. Examples of aromatic heterocyclic groups include groups obtained by removing two hydrogen atoms from five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, and furan, or six-membered aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The aromatic heterocyclic group may also be a group obtained by removing two hydrogen atoms from a fused ring compound (e.g., indole, quinoline, isoquinoline, etc.) having a structure in which the five-membered aromatic heterocyclic compound or the six-membered aromatic heterocyclic compound is condensed with at least one selected from the group consisting of the five-membered aromatic heterocyclic compound, the six-membered aromatic heterocyclic compound, aromatic hydrocarbons (e.g., benzene, naphthalene, etc.), cycloalkanes (e.g., cyclopentane, cyclohexane, etc.), and non-aromatic heterocyclic compounds (e.g., five-membered non-aromatic heterocyclic compounds such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.).

[0101] L Ｍ１ may contain other divalent groups in addition to the aromatic group. Examples of the other divalent groups include -CO-, -O-, -S-, -SO-, and -SO ２ -, an alkylene group, a cycloalkylene group, an alkenylene group, and groups in which a plurality of these groups are linked together. Ｍ１ When contains another divalent group, the other divalent group is preferably located closer to the main chain of the resin (A) than the aromatic group.

[0102] R １４ , R １５ and R １６ The alkyl group represented by R may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. １４ , R １５ and R １６ In the alkyl group represented by the formula (I), the methylene group may be substituted with at least one of —CO— and —O—. １４ , R １５ and R １６ The cycloalkyl group represented by the formula (I) may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or may be a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. １４ , R １５ and R １６ The number of carbon atoms in the aryl group represented by R is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 14. １４ , R １５ and R １６ The aryl group represented by R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. １４ , R １５ and R １６ The aralkyl group represented by the formula (I) is the same as the above-mentioned R １４ , R １５ and R １６

[0046] One hydrogen atom in the alkyl group represented by the formula １４ , R １５ and R １６ Preferred are groups substituted with an aryl group (preferably a phenyl group) represented by the following formula: and examples thereof include a benzyl group. １４ , R １５ and R １６The alkenyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably 2 to 5, and more preferably 2 to 3. The alkenyl group is preferably a vinyl group.

[0103] R １４ , R １５ and R １６ Two of the R may be bonded to form a ring. １４ , R １５ and R １６ The ring formed by bonding two of these is preferably a cycloalkyl ring. The cycloalkane ring may be a monocyclic cycloalkane ring or a polycyclic cycloalkane ring. The cycloalkane ring is preferably a monocyclic cycloalkane ring having 5 to 6 carbon atoms. In the cycloalkane ring, one or more of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

[0104] Each of the above groups in formula (M-1) may have a substituent, and examples of the substituent include the above-mentioned substituent T.

[0105] Specific examples of the repeating unit represented by formula (M-1) are shown below, but are not limited to these.

[0106]

[0107] The repeating unit represented by the above formula (M-2) will be explained. ２１ , R ２２ and R ２３ The explanation, specific examples and preferred ranges of R in the above formula (M-1) are １１ , R １２ and R １３ It is the same as L Ｍ２ The explanation, specific examples and preferred ranges of L in the above formula (M-1) Ｍ１ It is the same as R ２４ , R ２５ and R ２６The explanation, specific examples and preferred ranges of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by the formula (M-1) are as follows: １４ , R １５ and R １６ It is the same as R ２５ and R ２６ may be bonded to form a ring. ２５ and R ２６ The ring formed by bonding of L is preferably a non-aromatic ring, more preferably a non-aromatic ring having 5 to 8 ring atoms. Ｍ２ The aromatic group contained in R ２２ or R ２４ may be bonded to form a ring. Ｍ２ The aromatic group contained in R ２２ or R ２４ The ring formed by bonding is preferably a non-aromatic ring, more preferably a non-aromatic ring having 5 to 8 ring atoms.

[0108] Each of the above groups in formula (M-2) may have a substituent, and examples of the substituent include the above-mentioned substituent T.

[0109] Specific examples of the repeating unit represented by formula (M-2) are shown below, but are not limited to these.

[0110]

[0111] The repeating unit represented by the above formula (M-3) will be explained. ３１ , R ３２ and R ３３ The explanation, specific examples and preferred ranges of R in the above formula (M-1) are １１ , R １２ and R １３ It is the same as L Ｍ３ The explanation, specific examples and preferred ranges of L in the above formula (M-1) Ｍ１ It is the same as R ３４ , R ３５ and R ３６The explanation, specific examples and preferred ranges of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by the formula (M-1) are as follows: １４ , R １５ and R １６ It is the same as R ３５ and R ３６ may be bonded to form a ring. ３５ and R ３６ The ring formed by bonding is preferably a non-aromatic ring, more preferably a non-aromatic ring having 5 to 8 ring atoms.

[0112] Each of the above groups in formula (M-3) may have a substituent, and examples of the substituent include the above-mentioned substituent T.

[0113] Specific examples of the repeating unit represented by formula (M-3) are shown below, but are not limited to these.

[0114]

[0115] Specific examples of repeating units containing an acid-decomposable group other than the repeating unit (M) are shown below, but are not limited to these.

[0116]

[0117]

[0118] The content of repeating units having an acid-decomposable group in the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on the total repeating units in the resin (A). The content of repeating units having an acid-decomposable group in the resin (A) is preferably 80 mol% or less, more preferably 75 mol% or less, and even more preferably 70 mol% or less, based on the total repeating units in the resin (A). The repeating units having an acid-decomposable group in the resin (A) may be one type or two or more types. When two or more types are contained, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0119] (Repeating unit having an aromatic group) The resin (A) preferably has an aromatic group, and more preferably contains a repeating unit having an aromatic group (also referred to as "repeating unit (Ar)"). The repeating unit (Ar) may be a repeating unit having an acid-decomposable group, or may be a repeating unit different from the repeating unit having an acid-decomposable group.

[0120] The repeating unit (Ar) is preferably a repeating unit represented by the following formula (N-1).

[0121]

[0122] In formula (N-1), R １０１ , R １０２ and R １０３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group, provided that R １０２ is Ar Ａ may be bonded to form a ring, in which case R １０２ represents a single bond or an alkylene group. Ａ represents a single bond or a divalent linking group. Ａ represents an aromatic group; k represents an integer of 0 to 5;

[0123] R １０１ , R １０２ and R １０３ The alkyl group represented by R may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. １０１ , R １０２ and R １０３The cycloalkyl group represented by the formula (I) may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or may be a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. In the cycloalkyl group, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. １０１ , R １０２ and R １０３ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. １０１ , R １０２ and R １０３ The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0124] L in formula (N-1) Ａ represents a single bond or a divalent linking group. Ａ The divalent linking group represented by is not particularly limited, but examples thereof include —COO—, —CONR ６４ -, an alkylene group, or a group formed by combining two or more of these groups. ６４ represents a hydrogen atom or an alkyl group. The alkylene group is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. R ６４ When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0125] Ar in formula (N-1) Ａ represents an aromatic group, more specifically, a (k+1)-valent aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The description, specific examples, and preferred ranges of the divalent aromatic group when k is 1 are described in the above-mentioned formula (M-1) L Ｍ１ Ar is the same as the aromatic group contained in Ａ The aromatic group represented by may have a substituent. The substituent is not particularly limited, but examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; and aryl groups such as phenyl. When k is an integer of 2 or more, examples of the (k+1)-valent aromatic group include groups obtained by removing any (k-1) hydrogen atoms from a divalent aromatic group. Ar Ａ preferably represents an aromatic group having 6 to 18 carbon atoms, and more preferably represents a benzene ring group, a naphthalene ring group or a biphenylene ring group.

[0126] The repeating unit represented by formula (N-1) preferably has a hydroxystyrene structure. Ａ represents a benzene ring group. k represents an integer of 0 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0127] Specific examples of the repeating unit (Ar) are shown below, but are not limited to these. １ and G ２ each independently represents a hydrogen atom, a methyl group, a cyano group, a hydroxy group, or a hydroxymethyl group, and f1 represents an integer of 0 to 3.

[0128]

[0129] When the resin (A) contains a repeating unit (Ar), the content of the repeating unit (Ar) in the resin (A) is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units in the resin (A). Furthermore, the content of the repeating unit (Ar) in the resin (A) is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on the total repeating units in the resin (A). When the resin (A) contains a repeating unit (Ar), the repeating unit (Ar) in the resin (A) may be one type or two or more types. When two or more types are contained, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0130] (Repeating unit having no acid-decomposable group and having a fluorine atom, a bromine atom, or an iodine atom) In addition to the above-mentioned <repeating unit having an acid-decomposable group>, the resin (A) may have a repeating unit having no acid-decomposable group and having a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as "unit X"). The <repeating unit having no acid-decomposable group and having a fluorine atom, a bromine atom, or an iodine atom> is preferably different from other types of repeating units such as the above-mentioned repeating unit (Ar) and the below-mentioned <repeating unit having a lactone group, a sultone group, or a carbonate group> and <repeating unit having a photoacid-generating group>.

[0131] The unit X is preferably a repeating unit represented by formula (C).

[0132]

[0133] L ５ represents a single bond or an ester group. ９ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. １０represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group combining these. Specific examples of repeating units having a fluorine atom or an iodine atom include the repeating units described in paragraphs

[0116] to

[0117] of WO 2022 / 024928. The above descriptions are incorporated herein by reference.

[0134] When the resin (A) contains the unit X, the content of the unit X may be 5 mol% or more, or 10 mol% or more, based on all repeating units in the resin (A). The content of the unit X may be 50 mol% or less, or 40 mol% or less, based on all repeating units in the resin (A). It is also preferred that the resin (A) does not contain the unit X.

[0135] (Repeating unit having a lactone group, a sultone group, or a carbonate group) The resin (A) may have a repeating unit having a lactone group, a sultone group, or a carbonate group (hereinafter also referred to as "unit Y"). It is also preferable that unit Y does not have a hydroxyl group or an acid group such as a hexafluoropropanol group.

[0136] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure. Of these, a 5- to 7-membered lactone structure to which another ring structure is fused, forming a bicyclo or spiro structure, or a 5- to 7-membered sultone structure to which another ring structure is fused, forming a bicyclo or spiro structure, is more preferred. The carbonate group is preferably a cyclic carbonate ester group. For repeating units having a cyclic carbonate ester group, see, for example, paragraphs

[0127] to

[0133] of WO 2022 / 024928. The above descriptions are incorporated herein by reference.

[0137] Resin (A) preferably has a repeating unit having a lactone group, sultone group, or carbonate group obtained by removing one or more hydrogen atoms from a ring member atom of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-22), a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3), or a cyclic carbonate ester structure represented by any of the following formulas (CC1-1) to (CC1-2), and the lactone group, sultone group, or carbonate group may be directly bonded to the main chain. For example, the ring member atom of the lactone group, sultone group, or carbonate group may constitute the main chain of Resin (A). The lactone group, sultone group, and carbonate group may have a substituent.

[0138] R in the following structural formula Ｌ represents a substituent. Ｌ If there are multiple R Ｌ may be the same or different. Ｌ Examples of R include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group. e1 represents an integer of 0 to 4. When multiple e1s are present, the multiple e1s may be the same or different. When e1 is 2 or more, the multiple R Ｌ may be the same or different, and multiple R Ｌ They may be bonded to each other to form a ring.

[0139]

[0140] Examples of repeating units having a lactone group, a sultone group, or a carbonate group include repeating units represented by the following formula (AI-2).

[0141]

[0142] In formula (AI-2), Rb ０ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ０ Examples of groups that the alkyl group of Rb may have include a hydroxyl group and a halogen atom. ０Examples of the halogen atom in Rb include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ０ is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group formed by combining these. Among these, Ab is preferably a single bond or -Ab １ -CO ２ A linking group represented by - is preferred. １ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-22), a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3), or a group obtained by removing one hydrogen atom from a ring member atom of a cyclic carbonate structure represented by any of formulas (CC1-1) to (CC1-2).

[0143] When the resin (A) contains the unit Y, the content of the unit Y may be 1 mol% or more, or 10 mol% or more, based on all repeating units in the resin (A). The content of the unit Y may be 80 mol% or less, or 70 mol% or less, based on all repeating units in the resin (A). It is also preferred that the resin (A) does not contain the unit Y.

[0144] (Repeating unit having a photoacid generating group) The resin (A) may have a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid generating group"). Examples of the repeating unit having a photoacid generating group include a repeating unit represented by formula (4).

[0145]

[0146] R ４１ represents a hydrogen atom or a methyl group. ４１ represents a single bond or a divalent linking group. ４２ represents a divalent linking group. ４０represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

[0147] L ４１ represents a single bond or a divalent linking group, and preferably represents a single bond or an ester bond (—COO—).

[0148] L ４２ represents an alkylene group, a cycloalkylene group, an arylene group, —O—, —CO—, —S—, —SO—, —SO ２ Preferably, the linking group is at least one selected from the group consisting of - and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group). The alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but preferably 1 to 10. The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but preferably 3 to 20, more preferably 5 to 15. The number of carbon atoms in the arylene group is not particularly limited, but preferably 6 to 20, more preferably 6 to 10. The alkylene group, cycloalkylene group, and arylene group may have a substituent, and examples of the substituent include the substituent T described above.

[0149] R ４０ is preferably a group represented by the following formula (S4-1).

[0150]

[0151] In formula (S4-1), Q － represents an acid residue, M ＋ represents a cation. * represents L ４１ The bond position of the acid residue is a group formed by dissociating a proton from an acid. － is a carboxylate anion group (COO － ), sulfonate anion group (SO ３ － ), or a sulfonamide group (N － -SO ２ R Ｎ１ It is expressed as: R Ｎ１represents an organic group, and examples thereof include organic groups having 1 to 10 carbon atoms, and an alkyl group, a fluoroalkyl group, or an aryl group is preferred. ) is preferred, and a sulfonate anion group is more preferred. ＋ The explanation, specific examples and preferred ranges of M in the explanation of compound (B) to be described later. ＋ is the same as

[0152] Specific examples of repeating units having a photoacid generating group include the repeating units described in

[0094] to

[0105] of JP 2014-041327 A, the repeating unit described in

[0094] of WO 2018 / 193954 A, and the repeating unit described in

[0138] of WO 2022 / 024928 A. The above descriptions are incorporated herein by reference.

[0153] Examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of JP 2014-041327 A and the repeating unit described in paragraph

[0094] of WO 2018 / 193954 A.

[0154] When the resin (A) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more, based on the total repeating units in the resin (A).Furthermore, the content of the repeating unit having a photoacid generating group is preferably 40 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less, based on the total repeating units in the resin (A).It is also preferable that the resin (A) does not contain a repeating unit having a photoacid generating group.

[0155] (Repeating unit represented by formula (V-1) or formula (V-2)) The resin (A) may have a repeating unit represented by the following formula (V-1) or formula (V-2). It is also preferable that the repeating unit represented by the following formula (V-1) and the repeating unit represented by the following formula (V-2) are different from the above-mentioned respective repeating units.

[0156]

[0157] In formulas (V-1) and (V-2), R ６ and R ７ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. As the alkyl group, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ represents an integer of 0 to 6. ４ represents an integer of 0 to 4. ４ represents a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or formula (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0158] (Repeating Unit for Reducing Mobility of Main Chain) Resin (A) may have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. The Tg may be greater than 90°C, greater than 100°C, greater than 110°C, or greater than 125°C. In order to achieve an excellent dissolution rate in a developer, the Tg may be 400°C or less or 350°C or less. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of repeating unit") is calculated by the following method. First, the Tg of a homopolymer consisting of only each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass proportion (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of these values ​​is used to determine the Tg (°C) of the polymer. The Bicerano method is described in "Prediction of Polymer Properties," Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0159] For the repeating units for reducing the mobility of the main chain, the contents of paragraphs

[0144] to

[0160] of WO 2022 / 024928 are incorporated herein by reference.

[0160] (Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group) The resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating units described above in <Repeating unit having a lactone group, a sultone group, or a carbonate group>. The preferred content is also as described above in <Repeating unit having a lactone group, a sultone group, or a carbonate group>.

[0161] The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs

[0081] to

[0084] of JP 2014-098921 A.

[0162] The resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted at the α-position with an electron-withdrawing group, with a carboxyl group being preferred. When the resin (A) contains a repeating unit having an alkali-soluble group, resolution is improved, particularly in contact hole applications. Examples of repeating units having an alkali-soluble group include those described in paragraphs

[0085] and

[0086] of JP 2014-098921 A.

[0163] (Repeating Unit Having an Alicyclic Hydrocarbon Structure and Not Exhibiting Acid Decomposability) Resin (A) may have a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. This can reduce elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include repeating units derived from 1-adamantyl(meth)acrylate, diamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, and cyclohexyl(meth)acrylate.

[0164] (Repeating Unit Represented by Formula (III) Having Neither a Hydroxyl Group nor a Cyano Group) The resin (A) may have a repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group.

[0165]

[0166] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a —CH ２ -O-Ra ２ represents a group. ２ represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of JP-A 2014-098921.

[0167] (Other repeating units) Furthermore, the resin (A) may have other repeating units other than the repeating units described above. The resin (A) may have a repeating unit selected from the group consisting of, for example, a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. Examples of such repeating units include those described in

[0170] of WO 2022 / 024928.

[0168] Regarding the resin (A), the contents of

[0171] to

[0172] of WO 2022 / 024928 can be further cited.

[0169] Resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (A), as a polystyrene equivalent value measured by GPC, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 20,000, and particularly preferably 5,000 to 15,000. The dispersity (also referred to as "molecular weight distribution," "Pd," or "Mw / Mn") of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0170] The content of resin (A) in the composition of the present invention is 20% by mass or more, preferably 40.0 to 99.9% by mass, and more preferably 60.0 to 95.0% by mass, based on the total solid content of the composition of the present invention. Resin (A) may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0171] [Compound (B) that generates an acid upon irradiation with actinic rays or radiation] The composition of the present invention preferably contains a compound (B) (also simply referred to as "compound (B)") that generates an acid upon irradiation with actinic rays or radiation. Compound (B) is a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation. Compound (B) is also referred to as a "photoacid generator." The photoacid generator may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer. Furthermore, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. There is no particular lower limit, but a molecular weight of 100 or more is preferred. When the photoacid generator is in the form of being incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A). When the resin (A) does not have the repeating unit having the photoacid generating group described above, the composition of the present invention preferably contains a compound (B) that is a compound different from the resin (A). When the resin (A) has a repeating unit having a photoacid generating group, the composition of the present invention may or may not contain a separate compound (B). The photoacid generator is also preferably in the form of a low molecular weight compound. The photoacid generator is preferably a compound that generates an acid having a pKa of less than 0 upon irradiation with actinic rays or radiation, and more preferably a compound that generates an acid having a pKa of -15 or more and less than -1.

[0172] Examples of the photoacid generator include "M ＋ X － ", and it is preferably a compound that generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0173] "M ＋ X－ In the compound represented by the formula ", M ＋ represents a cation, preferably an organic cation. The organic cation is not particularly limited. The valence of the organic cation may be monovalent or divalent or higher. Among these, the organic cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0174]

[0175] In the above formula (ZaI), R ２０１ , R ２０２ , and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group represented by R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are some examples.

[0176] Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) described below.

[0177] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ is an arylsulfonium cation, in which at least one of R is an aryl group. ２０１ ~R ２０３may all be aryl groups, or R ２０１ ~R ２０３ A part of R may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ is an aryl group, and R ２０１ ~R ２０３ The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of the above include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and —CH ２ -CH ２ -O-CH ２ -CH ２ The arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0178] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group optionally contained in the arylsulfonium cation is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0179] R ２０１ ~R ２０３ Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 14 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, and phenylthio groups. The above substituents may further have substituents if possible, and it is also preferred that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents form an acid-decomposable group in any combination. Note that the acid-decomposable group is intended to be a group that decomposes under the action of acid to generate a polar group, and is preferably a structure in which the polar group is protected with a group that leaves under the action of acid. The above polar groups and leaving groups are as described above.

[0180] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation represented by the formula (ZaI) R ２０１ ~R ２０３ are each independently a cation representing an organic group that does not have an aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. ２０１ ~R ２０３ The number of carbon atoms of the organic group not having an aromatic ring as R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0181] R ２０１ ~R ２０３ Examples of the alkyl group and cycloalkyl group in R include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３ may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. ２０１ ~R ２０３ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0182] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0183]

[0184] In formula (ZaI-3b), R １ｃ ~R ５ｃR each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ R each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ R each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. １ｃ ~R ７ｃ , and R ｘ and R ｙ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0185] R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0186] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙExamples of the group formed by bonding of R include alkylene groups such as butylene and pentylene. The methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0187] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ The ring formed by bonding together may have a substituent.

[0188] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0189]

[0190] In formula (ZaI-4b), l represents an integer of 0 to 2, and r represents an integer of 0 to 8. １３ represents a hydrogen atom, a halogen atom (for example, a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４represents a hydroxyl group, a halogen atom (for example, a fluorine atom or an iodine atom), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ When a plurality of R are present, each independently represents the above group such as a hydroxyl group. １５ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ may be bonded to each other to form a ring. １５ When two R are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. １５ are preferably alkylene groups and bonded to each other to form a ring structure. １５ The ring formed by bonding together may have a substituent.

[0191] In formula (ZaI-4b), R １３ , R １４ , and R １５ The alkyl group in R may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. １３ ~R １５ , and R ｘ and R ｙ It is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0192] Next, formula (ZaII) will be described. In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. ２０４ and R ２０５ The aryl group in R may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0193] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５ Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0194] Specific examples of organic cations are shown below, but the present invention is not limited to these.

[0195]

[0196]

[0197] "M ＋ X － In the compound represented by the formula "X －represents an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0198] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0199] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0200] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0201] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0202] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0203] An example of the sulfonylimide anion is a saccharin anion.

[0204] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0205] Other non-nucleophilic anions include, for example, phosphorus fluorides (e.g., PF ６－ ), boron fluorides (e.g., BF ４ － ), and antimony fluorides (e.g., SbF ６ － ) are listed.

[0206] Preferred non-nucleophilic anions include aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which an alkyl group is substituted with a fluorine atom, and tris(alkylsulfonyl)methide anions in which an alkyl group is substituted with a fluorine atom. Among these, perfluoroaliphatic sulfonate anions (preferably having 4 to 8 carbon atoms) and benzenesulfonate anions having a fluorine atom are more preferred, and nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluorobenzenesulfonate anions, and 3,5-bis(trifluoromethyl)benzenesulfonate anions are even more preferred.

[0207] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0208]

[0209] In formula (AN1), R １ and R ２ each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred. Examples of groups 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. Examples of groups that are not electron-withdrawing groups include, each independently, -R', -OH, -OR', -OCOR', -NH ２ , -NR' ２ , —NHR′, or —NHCOR′ is preferred, where R′ is a monovalent hydrocarbon group.

[0210] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Among these, R １ and R ２ are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0211] L represents a divalent linking group. When a plurality of L's are present, they may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２ Examples of the divalent linking group include -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these groups. Among these, examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, or -SO ２ - or -COO-alkylene group- is more preferred.

[0212] As L, for example, a group represented by the following formula (AN1-1) is preferable: ａ - (CR２ａ ２ ) Ｘ -Q-(CR ２ｂ ２ ) Ｙ -* ｂ (AN1-1)

[0213] In formula (AN1-1), * ａ is R in formula (AN1). ３ Represents the bonding position with * ｂ represents -C(R １ ) (R ２ X and Y each independently represent an integer of 0 to 10, preferably an integer of 0 to 3. R ２ａ and R ２ｂ R each independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ When there are multiple R ２ａ and R ２ｂ may be the same or different, provided that when Y is 1 or more, -C(R １ ) (R ２ )- and CR directly bonded ２ｂ ２ R in ２ｂ is other than a fluorine atom. Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ where X+Y in formula (AN1-1) is 1 or more, and R ２ａ and R ２ｂ are all hydrogen atoms, Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-*Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ Represents. Ａ is R in formula (AN1). ３ represents the bonding position on the side, and * Ｂ represents -SO in formula (AN1). ３ － represents the bonding position on the side.

[0214] In formula (AN1), R ３ represents an organic group. The organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (for example, a linear alkyl group), a branched group (for example, a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0215] Among them, R ３is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and / or nitrogen atom, etc.). The heteroatom may be substituted for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group. Among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent. The cycloalkyl group may be monocyclic (e.g., a cyclohexyl group) or polycyclic (e.g., an adamantyl group), and preferably has 5 to 12 carbon atoms. As the lactone group and sultone group, for example, a group in which one hydrogen atom has been removed from a ring atom constituting the lactone structure or sultone structure in any of the structures represented by the above-mentioned formulae (LC1-1) to (LC1-21) and the structures represented by the above-mentioned formulae (SL1-1) to (SL1-3) is preferred.

[0216] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0217] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0218]

[0219] In formula (AN2), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0220] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atoms. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and is preferably a fluorine atom or CF ３ It is more preferable that both Xf's are fluorine atoms.

[0221] R ４ and R ５ R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. ４ and R ５ If there are multiple R ４ and R ５ may be the same or different. ４ and R ５ The alkyl group represented by the formula (I) preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. ４ and R ５ is preferably a hydrogen atom.

[0222] L represents a divalent linking group, and is defined the same as L in formula (AN1).

[0223] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0224] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can further suppress the diffusion of acid. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0225] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon that contributes to ring formation) may be a carbonyl carbon.

[0226] The anion represented by formula (AN2) is SO ３ － -CF ２ -CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -CHF-CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -COO-(L) ｑ’ -W, SO ３ － -CF ２ -CF ２ -CH ２ -CH ２ - (L) ｑ -W or SO ３ － -CF ２ -CH(CF ３ ) -OCO-(L) ｑ’ -W is preferred. Here, L, q and W are the same as those in formula (AN2). q' represents an integer of 0 to 10.

[0227] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0228]

[0229] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and the -(D-B) group. Examples of the substituent that may further be had include a fluorine atom and a hydroxyl group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0230] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0231] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0232] As the non-nucleophilic anion, a disulfonamide anion is also preferred. The disulfonamide anion is, for example, N － (SO ２ -R ｑ ) ２ where R ｑ represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. ｑ may be bonded to each other to form a ring. ｑ The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0233] The organic anions may be used singly or in combination of two or more. Specific examples of the organic anions are shown below, but are not limited thereto.

[0234]

[0235] The compound (B) preferably has a group that is decomposed by the action of an acid, and is more preferably represented by the following formula (U-1).

[0236]

[0237] In formula (U-1), L Ｕ１ represents a single bond or a divalent linking group. Ｕ１ If there are multiple L Ｕ１ may be the same or different. Ｕ１ represents a group that decomposes under the action of an acid. Ｕ１ If there are multiple A's, Ｕ１ may be the same or different. g represents an integer of 1 to 5. X Ｕ１ represents a g+1 valent linking group. Ｕ１ ＋ represents a sulfonium ion or an iodonium ion.

[0238] In formula (U-1), L Ｕ１ represents a single bond or a divalent linking group. Ｕ１ Examples of the divalent linking group represented by are -CO-, -O-, -S-, -SO-, and -SO ２ -, hydrocarbon groups (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these groups are linked together. Ｕ１ is preferably an alkylene group, an arylene group, -arylene group-alkylene group having a fluorine atom or an iodine atom-, -COO-Rt- group, or -O-Rt- group. Rt represents an alkylene group or a cycloalkylene group. As the arylene group, a phenylene group is preferred. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6. As Rt, an alkylene group having 1 to 5 carbon atoms is preferred, and -CH ２ - group, -(CH ２ ) ２ - group or -(CH２ ) ３ The - group is more preferred.

[0239] L Ｕ１ is particularly preferably an arylene group, alkylene, or a single bond, and most preferably a phenylene group or a single bond.

[0240] In formula (U-1), A Ｕ１ represents a group that is decomposed by the action of an acid. The group that is decomposed by the action of an acid preferably has a structure in which a polar group is protected with a group that is eliminated by the action of an acid (leaving group).

[0241] Examples of the polar group include those described in the repeating unit having an acid-decomposable group of the resin (A), and among them, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferred, and a carboxyl group or a phenolic hydroxyl group is more preferred. Examples of the group that is eliminated by the action of an acid include the groups represented by formulas (Y1) to (Y4) described in the explanation of the resin (A).

[0242] In formula (U-1), g represents an integer of 1 to 5, and preferably an integer of 1 to 3.

[0243] In formula (U-1), X Ｕ１ represents a g+1 valent linking group. Ｕ１ is preferably an aromatic group, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a benzene ring group. Ｕ１ may have a substituent.

[0244] In formula (U-1), M Ｕ１ ＋ represents a sulfonium ion or an iodonium ion. Examples of the sulfonium ion and the iodonium ion include the cations represented by the above-mentioned formula (ZaI) and formula (ZaII), and the above-mentioned cations (ZaI-1), (ZaI-2), (ZaI-3b), and (ZaI-4b) are preferred.

[0245] The compound (B) is more preferably a compound represented by the following formula (U-2).

[0246]

[0247] In formula (U-2), L Ｕ１ represents a single bond or a divalent linking group. Ｕ１ If there are multiple L Ｕ１ may be the same or different. Ｕ１ represents a group that decomposes under the action of an acid. Ｕ１ If there are multiple A's, Ｕ１ may be the same or different. Ｕ１ represents a substituent. Ｕ１ If there are multiple R Ｕ１ may be the same or different. Ｕ１ If there are multiple R Ｕ１ may be bonded to form a ring. g1 represents an integer of 1 to 5. g2 represents an integer of 0 to 4. M Ｕ１ ＋ represents a sulfonium ion or an iodonium ion.

[0248] L in formula (U-2) Ｕ１ , A Ｕ１ and M Ｕ１ ＋ The explanation, specific examples and preferred ranges of are respectively based on L in the above formula (U-1). Ｕ１ , A Ｕ１ and M Ｕ１ ＋ In formula (U-2), g1 represents an integer of 1 to 5, and preferably an integer of 1 to 3. In formula (U-2), g2 represents an integer of 0 to 4, and preferably an integer of 0 to 2, and particularly preferably 0. R in formula (U-2) Ｕ１Preferably, represents a substituent other than a group that decomposes under the action of an acid, and more preferably represents an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. The alkyl group may have a substituent. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. In the cycloalkyl group, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably a phenyl group or a naphthyl group. The aryl group may have a substituent.

[0249] The anion moiety (M Ｕ１ ＋ Examples of the part other than the part (part other than the part) are shown below, but are not limited to these.

[0250]

[0251] It is also preferable that the photoacid generator is at least one selected from the group consisting of compounds (I) to (II).

[0252] (Compound (I)) Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing the first acidic moiety derived from the structural moiety X and the second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation. Structural moiety X: Anionic moiety A １ － and the cationic moiety M １ ＋ and by irradiation with actinic rays or radiation, HA １ Structural moiety Y: anionic moiety A, which forms a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋ and by irradiation with actinic rays or radiation, HA ２ The compound (I) satisfies the following condition I:

[0253] Condition I: In the compound (I), the cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cation moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by ２ and an acid dissociation constant a2 derived from the acidic site represented by the formula (I), and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0254] Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y, compound PI is "HA １ and H.A.２ The acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." More specifically, when the acid dissociation constant of the compound PI is calculated, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." １ － and H.A. ２ The pKa at which the compound becomes "a compound having the above formula (A)" is the acid dissociation constant a1, １ － and H.A. ２ "A compound having １ － and A ２ － The pKa at which the compound becomes "a compound having the above formula (I)" is the acid dissociation constant a2.

[0255] For example, when compound (I) is an acid-generating compound having two of the first acidic sites derived from the structural site X and one of the second acidic sites derived from the structural site Y, compound PI is a compound having "two HAs １ and one HA ２ When the acid dissociation constant of compound PI is calculated, compound PI corresponds to "a compound having one A １ － and one HA １ and one HA ２ and the acid dissociation constant when "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ The acid dissociation constant when the compound is a compound having two A's corresponds to the acid dissociation constant a1 described above. １ － and one HA ２ "Compound having two A １ － and A ２ － In other words, in the case of compound PI, the acid dissociation constant when the compound becomes a compound having the cation moiety M in the structural moiety X corresponds to the acid dissociation constant a2. １ ＋ H ＋ HA is replaced by１ When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by the formula (I), the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1. １ － and one HA １ and one HA ２ The acid dissociation constant when the compound is aa is defined as "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ When the acid dissociation constant when the compound becomes "a compound having the formula (I)" is ab, the relationship between aa and ab satisfies aa<ab.

[0256] The acid dissociation constants a1 and a2 are determined by the above-mentioned method for measuring an acid dissociation constant. The compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation. When compound (I) has two or more structural moieties X, the structural moieties X may be the same or different. In addition, when two or more of the above A １ － and two or more of the above M １ ＋ In compound (I), the above A １ － and the above A ２ － , and the above M １ ＋ and the above M ２ ＋ may be the same or different, but １ － and the above A ２ － are preferably different from each other.

[0257] In the compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

[0258] In the compound PI, the acid dissociation constant a2 is preferably not more than 20, more preferably not more than 15. The lower limit of the acid dissociation constant a2 is preferably not less than −4.0.

[0259] In the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably −20.0 or more.

[0260] Anion site A １ － and anionic moiety A ２ － is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6) shown below. １ － As the anionic moiety A, those capable of forming an acidic moiety with a small acid dissociation constant are preferred, and among these, any of formulas (AA-1) to (AA-3) is more preferred, and any of formulas (AA-1) and (AA-3) is even more preferred. ２ － As the anion moiety A １ － Preferably, it is one that can form an acidic site with a larger acid dissociation constant than the above, more preferably any of formulas (BB-1) to (BB-6), and even more preferably any of formulas (BB-1) and (BB-4). In the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R Ａ represents a monovalent organic group. ＡThe monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0261]

[0262]

[0263] Cationic moiety M １ ＋ and cationic moiety M ２ ＋ is a structural moiety containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. ＋ Examples of the organic cation include those represented by the following formula:

[0264] (Compound (II)) Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z upon irradiation with actinic rays or radiation. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

[0265] In compound (II), the definition of the structural moiety X and A １ － and M １ ＋ The definition of the structural moiety X in the compound (I) and the definition of A １ － and M １ ＋ The definition and preferred embodiments are also the same as those given above.

[0266] In the compound (II), the cation moiety M in the structural moiety X １ ＋ H ＋ In the compound PII, the cationic moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by the formula (I) is the same as the acid dissociation constant a1 in the compound PI. In addition, when the compound (II) is, for example, a compound that generates an acid having two of the first acidic moieties derived from the structural moiety X and the structural moiety Z, the compound PII is a compound that generates an acid having two HAs. １ When the acid dissociation constant of this compound PII was calculated, it was found that the compound PII has "one A １ － and one HA １ and the acid dissociation constant when "a compound having one A １ － and one HA １ "Compound having two A １ － The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0267] The acid dissociation constant a1 is determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to the acid generated when the compound (II) is irradiated with actinic rays or radiation. The two or more structural moieties X may be the same or different. １ － and two or more of the above M １ ＋ may be the same or different.

[0268] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having electrons. Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The 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 formula:

[0269]

[0270] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Of these, a primary amine structure, a secondary amine structure, a tertiary amine structure, and a tertiary amine structure are preferred.

[0271] Examples of moieties other than cations that Compound (I) and Compound (II) may have are shown below.

[0272]

[0273]

[0274] The content of the photoacid generator is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, based on the total solid content of the composition of the present invention. The content of the photoacid generator is preferably 70.0% by mass or less, more preferably 50.0% by mass or less, and even more preferably 40.0% by mass or less, based on the total solid content of the composition of the present invention. One type of photoacid generator may be used, or two or more types may be used. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

[0275] [Acid Diffusion Controller] The composition of the present invention may further contain an acid diffusion controller other than the compound (D). The acid diffusion controller traps the acid generated from the photoacid generator or the like upon exposure and acts as a quencher to suppress the reaction of the acid-decomposable resin in unexposed areas due to excess generated acid. The type of acid diffusion controller is not particularly limited, and examples thereof include a basic compound (DA), a low-molecular-weight compound (DB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (DC) whose acid diffusion control ability is reduced or eliminated upon exposure to actinic rays or radiation. Examples of the compound (DC) include an onium salt compound (DD) of an acid that is weaker in acid than the acid generated from the photoacid generator, and a basic compound (DE) whose basicity is reduced or eliminated upon exposure to actinic rays or radiation. Specific examples of the basic compound (DA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, and specific examples of the basic compound (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs

[0137] to

[0155] of WO 2020 / 066824, and those described in paragraph

[0164] of WO 2020 / 066824, and specific examples of the low molecular weight compound (DB) having a nitrogen atom and having a group that leaves under the action of an acid include those described in paragraphs

[0156] to

[0163] of WO 2020 / 066824. Specific examples of the onium salt compound (DD) that is a weaker acid than the photoacid generator include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0276] In addition to the above, for example, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication No. 2016 / 0274458A1 can be suitably used as the acid diffusion controller.

[0277] When the composition of the present invention contains an acid diffusion controller other than compound (D), the content of the acid diffusion controller is preferably 0.1 to 15.0 mass%, more preferably 0.5 to 15.0 mass%, based on the total solids content of the composition of the present invention. The acid diffusion controller other than compound (D) may be used alone or in combination of two or more. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0278] [Hydrophobic Resin] The composition of the present invention may further contain a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed so as to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances. The effects of adding a hydrophobic resin include controlling the static and dynamic contact angles of the resist film surface with water, and suppressing outgassing.

[0279] The hydrophobic resin contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３ It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0280] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass% and more preferably 0.1 to 15.0 mass% based on the total solid content of the composition of the present invention. One type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0281] [Surfactant] The composition of the present invention may contain a surfactant. When a surfactant is contained, a pattern with better adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954.

[0282] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass%, more preferably 0.0005 to 1.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the composition of the present invention. One type of surfactant may be used, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0283] [Solvent] The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0284] Combining the above-mentioned solvent with the above-mentioned resin is preferable in terms of improving the coatability of the composition of the present invention and reducing the number of development defects in the pattern. The above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, and therefore can suppress unevenness in the film thickness of the resist film and the occurrence of precipitates during spin coating. Details of component (M1) and component (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306, the contents of which are incorporated herein by reference.

[0285] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0286] The content of the solvent in the composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass, which further improves the coatability of the composition of the present invention.

[0287] [Other Additives] The composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0288] The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less, which is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0289] [Actinic ray- or radiation-sensitive film, pattern forming method] The present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention. The actinic ray- or radiation-sensitive film of the present invention is preferably a resist film. The procedure of the pattern forming method using the composition of the present invention is not particularly limited, but preferably includes the following steps: Step 1: forming a resist film on a substrate using the composition of the present invention; Step 2: exposing the resist film; Step 3: developing the exposed resist film using a developer. The procedure of each of the above steps will be described in detail below.

[0290] (Step 1: Resist Film Forming Step) Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

[0291] A method for forming a resist film on a substrate using the composition of the present invention includes, for example, applying the composition of the present invention to a substrate. It is preferable to filter the composition of the present invention before application, if necessary. 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.

[0292] The composition of the present invention can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide) such as those used in the manufacture of integrated circuit elements by an appropriate application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed during spin application using a spinner is preferably 1,000 to 3,000 rpm (rotations per minute). After application of the composition of the present invention, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed below the resist film.

[0293] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or developing machine, and may also be performed using a hot plate 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 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0294] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming a finer pattern with higher precision. In particular, when EUV exposure is used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0295] A top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be uniformly applied to the resist film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of JP 2014-059543 A. For example, a top coat containing a basic compound such as that described in JP 2013-61648 A is preferably formed on the resist film. Specific examples of basic compounds that may be contained in the top coat include the basic compounds that may be contained in the composition of the present invention. It is also preferable that the top coat contain a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0296] (Step 2: Exposure Step) Step 2 is a step of exposing the resist film to light. Examples of exposure methods include irradiating the formed resist film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays, X-rays, and electron beams, and preferably have a wavelength of 250 nm or less, more preferably 220 nm or less, and far ultraviolet rays with a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Excimer laser (157 nm), EUV (13.5 nm), X-rays and electron beams are particularly preferred.

[0297] After exposure, it is preferable to bake (heat) the film before developing. Baking promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. 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 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like. This process is also called post-exposure baking.

[0298] (Step 3: Development Step) Step 3 is a step of developing the exposed resist film using a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0299] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of a substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispense nozzle is scanned at a constant speed (dynamic dispense method). Furthermore, after the development step, a step of stopping development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0300] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include aqueous alkaline solutions containing a quaternary ammonium salt, such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0301] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0302] The above-mentioned solvents may be mixed in plural, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0303] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0304] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse liquid.

[0305] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0306] The method for the rinsing step is not particularly limited, and examples include a method in which a rinsing solution is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinsing solution for a certain period of time (dipping method), and a method in which the rinsing solution is sprayed onto the substrate surface (spray method). The pattern formation method may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern by baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0307] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferred. The dry etching is preferably oxygen plasma etching.

[0308] The composition of the present invention and various materials used in the pattern formation method (e.g., solvents, developers, rinse solutions, anti-reflective coating compositions, top coat compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. There is no particular lower limit, and 0 mass ppt or more is preferred. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0309] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0310] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0311] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and a content of 0 ppt by mass or more is preferred.

[0312] A conductive compound may be added to an organic processing liquid such as a rinse solution to prevent breakdown of the chemical solution piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. There is no particular lower limit, but 0.01% by mass or more is preferred. For the chemical solution piping, for example, stainless steel (SUS), or various piping coated with antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used. Similarly, for the filters and O-rings, antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used.

[0313] [Method for Manufacturing an Electronic Device] The present specification also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of the present specification include those installed in electrical and electronic devices (such as home appliances, office automation (OA), media-related devices, optical devices, and communication devices).

[0314] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0315] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0316] <Resin> A-1 to A-12 were used as resin (A). The structures of A-1 to A-12 are shown below. The content ratio of the following repeating units (content relative to all repeating units in the resin) is a molar ratio. The weight average molecular weight (Mw) and dispersity (Pd = Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts converted into polystyrene). The content of the repeating units was １３ Measurement was performed by C-NMR (nuclear magnetic resonance).

[0317]

[0318]

[0319]

[0320] A synthesis example of A-1 is shown below. Other resins (A) were synthesized in the same manner.

[0321] (Synthesis of A-1) Cyclohexanone (57 g) was heated to 85°C under a nitrogen stream. To this solution, while stirring, a mixed solution of a monomer represented by the following formula M-1 (50.5 g), a monomer represented by the following formula M-2 (37.1 g), cyclohexanone (106 g), and 2,2'-azobisisobutyric acid dimethyl ester [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (8.6 g) was added dropwise over 3 hours to obtain a reaction solution. After completion of the dropwise addition, the reaction solution was stirred at 85°C for an additional 3 hours. The obtained reaction solution was allowed to cool and then reprecipitated with 4100 g of ethyl acetate / heptane (mass ratio 1:9), filtered, and the obtained solid was vacuum dried to obtain Resin A-1 (66 g).

[0322]

[0323] <Compound (B)> Compounds (B) (photoacid generators) B-1 to B-6 were used. The structures of B-1 to B-6 are shown below.

[0324]

[0325] <Compound (D)> D-1 to D-12 were used as compound (D). DX-1 to DX-3 were used as nitrogen-containing compounds other than compound (D). The structures of D-1 to D-12 and DX-1 to DX-3 are shown below. Table 1 also shows the formula weight of the portion corresponding to Ra in the above general formula (1) for each compound.

[0326]

[0327]

[0328]

[0329] A synthesis example of D-1 is shown below. Other compounds (D) were also synthesized in the same manner.

[0330] (Synthesis of D-1) 4-Hydroxypyridine (12.3 g) was dissolved in tetrahydrofuran (100 g) and then cooled to 0°C. Benzyl chloroformate (10.0 g) was added dropwise thereto, and the mixture was stirred at 0°C for 30 minutes, then heated to 25°C and stirred for an additional 1 hour. Water (100 g) and ethyl acetate (100 g) were added to the reaction solution, and the mixture was separated. The resulting organic layer was washed three times with water (100 g) each time. The resulting organic phase was then concentrated to obtain D-1 (11.2 g).

[0331]

[0332] <Acid Diffusion Controllers Other Than Compound (D)> C-1 to C-4 were used as acid diffusion controllers other than compound (D). The structures of C-1 to C-4 are shown below.

[0333]

[0334] <Hydrophobic Resin> P-1 was used as the hydrophobic resin. The structure of P-1 is shown below. The content ratio of the following repeating units (content relative to all repeating units in the resin) is a molar ratio. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The content of the repeating units was １３ Measurement was performed by C-NMR.

[0335]

[0336] <Surfactants> The surfactants used are as follows: W-1: Megafac F176 (manufactured by DIC Corporation; fluorine-based) W-2: Megafac R08 (manufactured by DIC Corporation; fluorine and silicone-based) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based) W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) W-5: KH-20 (manufactured by AGC Inc.) W-6: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

[0337] <Solvents> The solvents used are as follows: SL-1: Propylene glycol monomethyl ether acetate (PGMEA) SL-2: Propylene glycol monomethyl ether propionate SL-3: 2-heptanone SL-4: Ethyl lactate SL-5: Propylene glycol monomethyl ether (PGME) SL-6: Cyclohexanone SL-7: γ-butyrolactone SL-8: Propylene carbonate

[0338] <Preparation of Resist Compositions> The components shown in Table 2 were dissolved in the solvents shown in Table 2 in the amounts (g) shown in Table 2 to prepare solutions with a solids concentration of 2.5% by mass. These solutions were then filtered through a polyethylene filter with a pore size of 0.02 μm to obtain resist compositions Re-1 to Re-20 and Re-X1 to Re-X3. The types of compounds used in the solvents and their mass ratios are shown in Table 2. In Table 2, when two or more types of each component were used, the type and amount used are separated by " / ".

[0339]

[0340] Examples 1-1 to 1-20 and Comparative Examples 1-1 to 1-3 Coating of Resist Composition The resist composition thus prepared was applied to a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and then dried on a hot plate at 130°C for 300 seconds to obtain a resist film with a thickness of 100 nm. Note that similar results were obtained even when the Si wafer was replaced with a chromium substrate.

[0341] <Pattern Forming Method (1): EB Exposure, Alkali Development (Positive)> The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (manufactured by Advantest Corporation; F7000S, acceleration voltage 50 keV). At this time, lithography was performed so as to form a 1:1 line and space. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The wafer was then rotated at 4000 rpm for 30 seconds, baked at 95°C for 60 seconds, and dried.

[0342] <Pattern Forming Method (2): EUV Exposure, Alkali Development (Positive)> The wafer coated with the resist film obtained above was subjected to pattern exposure using an EUV exposure apparatus (Micro Exposure Tool, manufactured by Exitech, NA (numerical aperture) 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36) and an exposure mask (line / space = 1 / 1). After exposure, the wafer was heated on a hot plate at 100°C for 90 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. The wafer was then rotated at 4000 rpm for 30 seconds, baked at 95°C for 60 seconds, and dried.

[0343] <Evaluation: Resolution> The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). The limiting resolving power (the minimum line width at which lines and spaces (line:space = 1:1) are separately resolved) at the exposure dose when resolving a 1:1 line and space resist pattern with a line width of 50 nm was taken as the resolution (nm). The smaller this value, the higher the resolution. The results are shown in Table 3. The results when patterns were formed by pattern formation method (1) are listed in the "EB exposure" column. The results when patterns were formed by pattern formation method (2) are listed in the "EUV exposure" column.

[0344]

[0345] Examples 2-3, 2-12, 2-14, 2-16, 2-17, 2-19, and Comparative Example 2-3 Of the resist compositions prepared by the methods described above, those listed in Table 4 below were used. The resist compositions were applied in the same manner as in <Application of Resist Composition> above, to obtain wafers coated with a resist film.

[0346] <Pattern Forming Method (3): EB Exposure, Organic Solvent Development (Negative)> The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (manufactured by Advantest Corporation; F7000S, acceleration voltage 50 keV). At this time, lithography was performed so as to form a 1:1 line and space. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, and then developed with n-butyl acetate for 30 seconds, followed by spin drying to obtain a negative pattern.

[0347] <Pattern Forming Method (4): EUV Exposure, Organic Solvent Development (Negative)> The wafer coated with the resist film obtained above was subjected to pattern exposure using an EUV exposure apparatus (Micro Exposure Tool, manufactured by Exitech, NA (numerical aperture) 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36) and an exposure mask (line / space = 1 / 1). After exposure, the wafer was heated on a hot plate at 100°C for 90 seconds, and then developed with n-butyl acetate for 30 seconds, followed by spin drying to obtain a negative pattern.

[0348] The evaluation was carried out in the same manner as in the above-mentioned <Evaluation: Resolution>. The results are shown in Table 4. The results when a pattern was formed by pattern formation method (3) are shown in the "EB exposure" column. The results when a pattern was formed by pattern formation method (4) are shown in the "EUV exposure" column.

[0349]

[0350] The results in Tables 3 and 4 show that the resist compositions used in the examples are excellent in resolution.

[0351] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution. The present invention can also provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

[0352] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2024-032107) filed on March 4, 2024, the contents of which are incorporated herein by reference.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (D) represented by the following general formula (1): In general formula (1), Ra represents a nonionic organic group. Rb to Re each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, a halogen atom, a cyano group, an alkoxy group, an alkenyl group, or an alkynyl group. ArN represents a heteroaryl group having a nitrogen atom as a ring member, an aryl group having an amino group as a substituent, or a heteroaryl group having an amino group as a substituent. m and n each independently represent an integer of 0 to 2. L represents a linking group represented by any of the following general formulae (1-1) to (1-7): In general formulas (1-1) to (1-7), Rf, Rg, Rh, and Ri each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. *1 represents the carbon atom to which Rb is bonded or the bonding site with Ra in general formula (1). *2 represents the carbon atom to which Rd is bonded or the bonding site with ArN in general formula (1).

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the formula weight of Ra in the general formula (1) is 200 or more.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein Ra in the general formula (1) is an aromatic group.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, which contains a resin (A) that decomposes under the action of an acid and exhibits increased polarity.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein the resin (A) has an aromatic group.

6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5, wherein the resin (A) has a repeating unit represented by the following formula (N-1): In formula (N-1), R １０１ , R １０２ and R １０３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group, provided that R １０２ is Ar Ａ may be bonded to form a ring, in which case R １０２ represents a single bond or an alkylene group. Ａ represents a single bond or a divalent linking group. Ａ represents an aromatic group; k represents an integer of 0 to 5; 7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein the resin (A) contains at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (M-1), a repeating unit represented by the following formula (M-2), and a repeating unit represented by the following formula (M-3): In formula (M-1), R １１ , R １２ and R １３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ｍ１ represents a divalent linking group containing an aromatic group. １４ , R １５ and R １６ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. １４ , R １５ and R １６ In formula (M-2), two of R may be bonded to form a ring. ２１ , R ２２ and R ２３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ｍ２ represents a divalent linking group containing an aromatic group. ２４ , R ２５ and R ２６ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ２５ and R ２６ may be bonded to form a ring. Ｍ２ The aromatic group contained in R ２２ or R ２４ In formula (M-3), R ３１ , R ３２ and R ３３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ｍ３ represents a divalent linking group containing an aromatic group. ３４ and R ３５ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３６ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３５ and R ３６ may be bonded to form a ring.

8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising a compound (B) that generates an acid upon exposure to actinic rays or radiation.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8, wherein the compound (B) has a group that is decomposed by the action of an acid.

10. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8, wherein the compound (B) is represented by the following formula (U-1): In formula (U-1), L Ｕ１ represents a single bond or a divalent linking group. Ｕ１ If there are multiple L Ｕ１ may be the same or different. Ｕ１ represents a group that decomposes under the action of an acid. Ｕ１ If there are multiple A's, Ｕ１ may be the same or different. g represents an integer of 1 to 5. X Ｕ１ represents a g+1 valent linking group. Ｕ１ ＋ represents a sulfonium ion or an iodonium ion.

11. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8, wherein the compound (B) is represented by the following formula (U-2): In formula (U-2), L Ｕ１ represents a single bond or a divalent linking group. Ｕ１ If there are multiple L Ｕ１ may be the same or different. Ｕ１ represents a group that decomposes under the action of an acid. Ｕ１ If there are multiple A's, Ｕ１ may be the same or different. Ｕ１ represents a substituent. Ｕ１ If there are multiple R Ｕ１ may be the same or different. Ｕ１ If there are multiple R Ｕ１ may be bonded to form a ring. g1 represents an integer of 1 to 5. g2 represents an integer of 0 to 4. M Ｕ１ ＋ represents a sulfonium ion or an iodonium ion.

12. An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11.

13. A pattern forming method comprising the steps of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11, exposing the resist film to light, and developing the exposed resist film using a developer.

14. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 13.