Chemical solution, pattern formation method

Abstract

The present invention provides a chemical solution that, when used as an image development solution or a rinse solution to form a pattern, results in excellent resolution of the obtained pattern and also excellent suppression of defect generation. The chemical solution of the present invention includes an aromatic hydrocarbon, an organic solvent other than the aromatic hydrocarbon, and a metal X, wherein: the aromatic hydrocarbon consists of hydrogen atoms and carbon atoms; the content of the aromatic hydrocarbon is no more than 1 mass% relative to the total mass of the chemical solution; the organic solvent includes an aliphatic hydrocarbon; the metal X is at least one metal selected from the group consisting of Al, Fe, and Ni; and the mass ratio of the content of the aromatic hydrocarbon to the content of the metal X is 5.0×104 to 2.0×1010.

Description

[Technical Field]

[0001] The present invention relates to a chemical solution and a pattern forming method. [Background technology]

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) or LSICs (Large Scale Integrated Circuits), microfabrication has been performed using a photolithography process with a photoresist composition. In such photolithography processes, for example, a coating film is formed using a photoresist composition (a photosensitive or radiation-sensitive resin composition), the resulting coating film is exposed to light, then developed with a developer to obtain a pattern, and finally the cured film after development is washed with a rinsing solution.

[0003] For example, Patent Document 1 discloses a developer solution containing an organic solvent, which is a good solvent for the resist film before exposure (S-1) and a poor solvent for the resist film before exposure (S-2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2011-065105 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The present inventors found that when forming patterns using a developer as described in Patent Document 1 as a developer or rinse solution, it was difficult to achieve both high resolution and defect suppression in the resulting patterns. In particular, it was difficult to achieve both of these performances when forming higher-resolution patterns.

[0006] Therefore, an object of the present invention is to provide a chemical solution that is excellent in the resolution of a pattern obtained when forming a pattern by using it as a developing solution or a rinsing solution and is also excellent in suppressing the generation of defects.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0008] 〔1〕 A chemical solution containing an aromatic hydrocarbon, an organic solvent other than the aromatic hydrocarbon, and a metal X, wherein the aromatic hydrocarbon consists only of hydrogen atoms and carbon atoms, the content of the aromatic hydrocarbon is 1% by mass or less based on the total mass of the chemical solution, the organic solvent contains an aliphatic hydrocarbon, the metal X is at least one metal selected from the group consisting of Al, Fe, and Ni, the mass ratio of the content of the aromatic hydrocarbon to the content of the metal X is 5.0×10 ~2.0×10 10 A chemical solution. 〔2〕 The chemical solution according to 〔1〕, which is used as a developing solution or a rinsing solution. 〔3〕 The aromatic hydrocarbon contains at least one selected from the group consisting of C 10 H 14 , C 11 H 16 and C 10 H 12 The chemical solution according to 〔1〕 or 〔2〕, wherein the content of the aromatic hydrocarbon is 5 to 2000 mass ppm based on the total mass of the chemical solution. 〔4〕 Furthermore, it contains a sulfur-containing compound, wherein the aromatic hydrocarbon contains at least one selected from the group consisting of C 10 10 H 14 , C 11 H 16 and C​10 H 12 It includes at least one selected from the group consisting of, C above 10 H 14 Content of the above C 11 H 16 The content and the above C 10 H 12 A drug solution according to any one of [1] to [3], wherein the content of each of the above is greater than the content of the sulfur-containing compound. [5] Furthermore, it contains sulfur-containing compounds, The chemical solution according to any one of [1] to [4], wherein the mass ratio of the content of the aromatic hydrocarbon to the content of the sulfur-containing compound is 1 or more. [6] A chemical solution according to any one of [1] to [5], containing three or more of the above aromatic hydrocarbons. [7] Furthermore, it contains water, The drug solution described in any one of [1] to [6], wherein the water content is 20 to 1000 ppm by mass relative to the total mass of the drug solution. [8] The drug solution according to any one of [1] to [7], wherein the content of at least one of the above Al, above Fe, and above Ni is 0.1 to 100 ppt by mass with respect to the total mass of the drug solution. [9] The drug solution according to any one of [1] to [8], wherein the above-mentioned aliphatic hydrocarbon comprises at least one selected from the group consisting of decane, undecane, dodecane, and methyldecane.

[10] Furthermore, it contains alcohol compounds, The chemical solution according to any one of [1] to [9], wherein the mass ratio of the content of the aromatic hydrocarbon to the content of the alcohol compound is 0.001 to 200.

[11] The drug solution according to

[10] , wherein the alcohol compound comprises at least one selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, and 2-methyl-1-butanol.

[12] The chemical solution according to any one of [1] to

[11] , wherein the above organic solvent further contains an ester-based solvent.

[13] A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, An exposure step for exposing the above-mentioned resist film, A pattern forming method including a developing step of developing the exposed resist film using a developer, The chemical solution used as the above-mentioned developing solution is one of the solutions listed in [1] to

[12] .

[14] A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, An exposure step for exposing the above-mentioned resist film, The above-mentioned exposed resist film is developed using butyl acetate in a development step, In a pattern forming method that includes a washing step of washing with a rinsing solution after the developing step, The chemical solution used as the rinse solution described above, one of the solutions listed in [1] to

[12] .

[15] A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, An exposure step for exposing the above-mentioned resist film, The above-mentioned exposed resist film is developed using a developing solution, In a pattern forming method that includes a washing step of washing with a rinsing solution after the developing step, A chemical solution described in any one of [1] to

[12] , used as the developer and rinse solution.

[16] A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, The exposure process involves exposing the resist film, The developed process involves developing the exposed resist film using a developer solution, A pattern forming method comprising a washing step of washing with a rinsing solution after the developing step, One of the chemicals [1] to

[12] is used as the developing solution and the rinsing solution. A pattern forming method in which the content of aliphatic hydrocarbons in the chemical solution used as a rinse solution relative to the organic solvent is greater than the content of aliphatic hydrocarbons in the chemical solution used as a developer relative to the organic solvent. [Effects of the Invention]

[0009] According to the present invention, when used as a developer or rinse solution to form a pattern, it is possible to provide a chemical solution that exhibits excellent resolution of the resulting pattern and excellent ability to suppress the occurrence of defects. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, unless otherwise specified, the notation of groups (atomic groups) includes both substituted and unsubstituted groups when neither is indicated. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" refers to a group containing at least one carbon atom. Unless otherwise specified, the substituents are preferably monovalent. In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet light such as those from excimer lasers, extreme ultraviolet light, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. The bonding direction of divalent groups as expressed herein is not limited unless otherwise specified. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may also be -CO-O- or -O-CO-. Furthermore, the above compound may also be "X-CO-OZ" or "XO-CO-Z".

[0011] In this specification, "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate. "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (Mw / Mn, hereinafter also referred to as "molecular weight distribution") of the resin are polystyrene-converted values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (HLC-8120GPC, manufactured by Tosoh Corporation) instrument (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation), column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0012] In this specification, "ppm" means "parts-per-million (10 -6) means, and "ppb" means "parts-per-billion (10 -9 )", and "ppt" means "parts-per-trillion (10 -12 )".

[0013] In this specification, the acid dissociation constant (pKa) represents the pKa in an aqueous solution. Specifically, using the following software package 1, a value based on Hammett's substituent constant and a database of known literature values can be obtained by calculation. All the pKa values described in this specification indicate values obtained by calculation using this software package.

[0014] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994 - 2007 ACD / Labs).

[0015] On the other hand, pKa can also be determined by the molecular orbital calculation method. As a specific method, there is a method of calculating by calculating the dissociation free energy of H + in an aqueous solution based on a thermodynamic cycle. Regarding the calculation method of the dissociation free energy of H + , for example, it can be calculated by DFT (density functional theory), but various other methods have been reported in the literature and the like, and it is not limited to this. As software that can perform DFT, for example, Gaussian16 can be mentioned.

[0016] As described above, the pKa in this specification indicates a value obtained by calculation using software package 1 based on Hammett's substituent constant and a database of known literature values. However, when pKa cannot be calculated by this method, the value obtained by Gaussian16 based on DFT (density functional theory) shall be adopted. In addition, the pKa in this specification indicates "pKa in an aqueous solution" as described above. However, when the pKa in an aqueous solution cannot be calculated, "pKa in a dimethyl sulfoxide (DMSO) solution" shall be adopted.

[0017] In this specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0018] In this specification, the solid content means the components forming the resist film and does not include a solvent. Further, any component that forms the resist film, even if its property is liquid, is regarded as a solid content.

[0019] [Chemical solution] The chemical solution is a chemical solution containing an aromatic hydrocarbon, an organic solvent other than the aromatic hydrocarbon, and metal X, where the aromatic hydrocarbon consists only of hydrogen atoms and carbon atoms, the content of the aromatic hydrocarbon is 1% by mass or less with respect to the total mass of the chemical solution, the organic solvent contains an aliphatic hydrocarbon, metal X is at least one metal selected from the group consisting of Al, Fe, and Ni, the mass ratio of the content of the aromatic hydrocarbon to the content of metal X is 5.0×10 4 ~2.0×10 10 or less.

[0020] When using the chemical solution having the above configuration, although the detailed mechanism of action that is excellent in pattern resolution and also excellent in suppressing the occurrence of defects is not clear, the present inventors presume as follows. Examples of the characteristic points of the above chemical solution include, for example, the mass ratio of the content of the aromatic hydrocarbon to the content of metal X. When the above mass ratio is within a predetermined range, when forming a pattern using the above chemical solution as a developer or a rinse solution, for example, it is presumed that while suppressing the deterioration of resolution due to the aromatic hydrocarbon, an increase in the number of defects due to metal X can be suppressed, so that both pattern resolution and suppression of the occurrence of defects can be achieved. Hereinafter, the phrase "the effects of the present invention are superior" refers to the superiority of at least one of the effects of superior pattern resolution and superior defect suppression.

[0021] The chemical solution is preferably used in the developing process and the rinsing process, which will be described later. In other words, the chemical solution is preferably used as a developer or a rinse solution. The following details the various components that the drug solution may contain.

[0022] <<First Embodiment>> The first embodiment of the drug solution will be described in detail below. The first embodiment of the chemical solution is preferably used as a developing solution.

[0023] [Aromatic hydrocarbons] The chemical solution contains aromatic hydrocarbons. "Aromatic hydrocarbons" refer to hydrocarbons that consist only of hydrogen and carbon atoms and have an aromatic ring. Aromatic hydrocarbons are not included in organic solvents. The aromatic hydrocarbon content is 1% by mass or less relative to the total mass of the chemical solution, preferably 1 to 5000 ppm by mass, more preferably 5 to 2000 ppm by mass, and even more preferably 5 to 200 ppm by mass. If the aromatic hydrocarbon contains two or more types of aromatic hydrocarbons, it is preferable that the total content of these two or more aromatic hydrocarbons is within the above range.

[0024] The number of carbon atoms in the aromatic hydrocarbon is preferably 6 to 30, more preferably 6 to 20, and even more preferably 10 to 12. The aromatic rings in aromatic hydrocarbons may be monocyclic or polycyclic. The number of members in the aromatic ring of an aromatic hydrocarbon is preferably 6 to 12, more preferably 6 to 8, and even more preferably 6. The aromatic ring of the aromatic hydrocarbon may have further substituents. Examples of substituents include alkyl groups, alkenyl groups, and groups combining them. The alkyl group and alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group and alkenyl group is preferably 1 to 10, and more preferably 1 to 5. Examples of aromatic rings in aromatic hydrocarbons include optionally substituted benzene rings, optionally substituted naphthalene rings, and optionally substituted anthracene rings, with optionally substituted benzene rings being preferred. In other words, benzene, which may have substituents, is preferred as the aromatic hydrocarbon.

[0025] Aromatic hydrocarbons are C 10 H 14 , C 11 H 16 and C 10 H 12 Preferably, it includes at least one selected from the group consisting of the following: Furthermore, as aromatic hydrocarbons, compounds represented by formula (c) are also preferred.

[0026] [ka]

[0027] In formula (c), R c represents a substituent. c represents an integer from 0 to 6.

[0028] R c represents a substituent. R c The substituents represented are preferably alkyl groups or alkenyl groups. The alkyl group and alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group and alkenyl group is preferably 1 to 10, and more preferably 1 to 5. R c If there are multiple instances, Rc They may be the same or different, and R c They may be bonded to each other to form a ring. Also, R c (R c When there are a plurality of them, a part or all of the plurality of R c and the benzene ring in formula (c) may be condensed to form a condensed ring.

[0029] c represents an integer from 0 to 6. c is preferably an integer from 1 to 5, more preferably an integer from 1 to 4.

[0030] The molecular weight of the aromatic hydrocarbon is preferably 50 or more, more preferably 100 or more, and still more preferably 120 or more. The upper limit is preferably 1000 or less, more preferably 300 or less, and still more preferably 150 or less.

[0031] Examples of the aromatic hydrocarbon include C such as 1,2,4,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, 1,2,3,5-tetramethyl-benzene, and 1-ethyl-2,4-dimethyl-benzene 10 H 14 ; C such as 1-methyl-4-(1-methylpropyl)-benzene and (1-methybutyl)-benzene 11 H 16 ; C such as 1-methyl-2-(2-propenyl)-benzene and 1,2,3,4-tetrahydro-naphthalene 10 H 12 and the like. Examples of the aromatic hydrocarbon include 1,2,4,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-methyl-4-(1-methylpropyl)-benzene, and C 10 H 12Preferably, 1-ethyl-3,5-dimethylbenzene or 1,2,3,5-tetramethylbenzene is more preferred.

[0032] Aromatic hydrocarbons may be used individually or in combination of two or more. The chemical solution preferably contains two or more aromatic hydrocarbons, more preferably three or more aromatic hydrocarbons, even more preferably three to eight aromatic hydrocarbons, and particularly preferably three or four aromatic hydrocarbons. One example of a method for measuring the content of aromatic hydrocarbons is the method for measuring the content of organic solvents, which will be described later. Methods for adjusting the aromatic hydrocarbon content include, for example, selecting raw materials with a low aromatic hydrocarbon content as constituent materials for various components, distilling under conditions that suppress contamination by lining the equipment with Teflon®, and adding aromatic hydrocarbons.

[0033] [Organic solvents] The chemical solution contains organic solvents other than the aromatic hydrocarbons mentioned above. In this specification, the above-mentioned organic solvent refers to an organic solvent other than the aromatic hydrocarbons described above, and is contained in an amount of 8,000 ppm by mass or more relative to the total mass of the chemical solution. Furthermore, organic solvents contained in an amount of less than 8,000 ppm by mass relative to the total mass of the chemical solution are considered organic impurities and not organic solvents. In other words, the alcohol compounds described later are not included in organic solvents and are considered organic impurities.

[0034] <Aliphatic hydrocarbons> Organic solvents include aliphatic hydrocarbons. "Aliphatic hydrocarbons" refer to hydrocarbons that consist only of hydrogen and carbon atoms and do not have an aromatic ring. Aliphatic hydrocarbons may be linear, branched, or cyclic (monocyclic or polycyclic), with linear being preferred. Furthermore, the aliphatic hydrocarbons may be either saturated or unsaturated. Aliphatic hydrocarbons often have two or more carbon atoms, preferably five or more, and more preferably ten or more. The upper limit is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 13 or less. Specifically, the number of carbon atoms in the aliphatic hydrocarbon is preferably 11.

[0035] Examples of aliphatic hydrocarbons include pentane, isopentane, hexane, isohexane, cyclohexane, ethylcyclohexane, methylcyclohexane, heptane, octane, isooctane, nonane, decane, methyldecane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, hepradecane, 2,2,4-trimethylpentane, and 2,2,3-trimethylhexane. The aliphatic hydrocarbon preferably contains an aliphatic hydrocarbon having 5 or more carbon atoms (preferably 20 or fewer carbon atoms), more preferably contains an aliphatic hydrocarbon having 10 or more carbon atoms (preferably 13 or fewer carbon atoms), even more preferably contains at least one selected from the group consisting of decane, undecane, dodecane, and methyldecane, and particularly preferably contains undecane.

[0036] The aliphatic hydrocarbon content is preferably 0.8% by mass or more and less than 100% by mass, more preferably 1 to 50% by mass, even more preferably 3 to 30% by mass, and particularly preferably 8 to 18% by mass, based on the total mass of the drug solution. The aliphatic hydrocarbon content is preferably 0.8% to 100% by mass, more preferably 1 to 100% by mass, even more preferably 2 to 100% by mass, even more preferably 2 to 50% by mass, particularly preferably 3 to 30% by mass, and most preferably 8 to 18% by mass, relative to the total mass of the organic solvent.

[0037] <Ester-based solvents> The organic solvent preferably further contains an ester-based solvent. The ester solvent may be linear, branched, or cyclic (monocyclic or polycyclic), with linear being preferred. The number of carbon atoms in ester solvents is often 2 or more, preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more. The upper limit is often 20 or less, preferably 10 or less, more preferably 8 or less, and particularly preferably 7 or less. Specifically, the number of carbon atoms in the ester solvent is preferably 6.

[0038] Examples of ester solvents include butyl acetate, isobutyl acetate, tertbutyl acetate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, hexyl acetate, methoxybutyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, amyl formate, isoamyl formate, methyl lactate, ethyl lactate, butyl lactate, propyl lactate, methyl 2-hydroxyisobutyrate, ethyl butyrate, ethyl isobutyrate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, and isobutyl propionate. The ester solvent preferably contains at least one selected from the group consisting of butyl acetate, isobutyl acetate, ethyl acetate, and hexyl acetate, and more preferably contains butyl acetate.

[0039] The content of the ester solvent is preferably 10% by mass or more and less than 100% by mass, more preferably 60-99% by mass, even more preferably 60-95% by mass, and particularly preferably 80-90% by mass, based on the total mass of the chemical solution. The content of the ester solvent is preferably 10% by mass or more and less than 100% by mass, more preferably 60-99% by mass, even more preferably 60-95% by mass, and particularly preferably 80-90% by mass, relative to the total mass of the organic solvent.

[0040] The organic solvent preferably contains aliphatic hydrocarbons and ester solvents, and more preferably consists solely of aliphatic hydrocarbons and ester solvents. When the organic solvent contains aliphatic hydrocarbons and ester solvents, the content of ester solvents relative to the content of aliphatic hydrocarbons (ester solvent content / aliphatic hydrocarbon content) is preferably 0.01 or more, more preferably 1 to 35, and even more preferably 4 to 20. The total content of aliphatic hydrocarbons and ester solvents is preferably 10% by mass or more and less than 100% by mass, more preferably 80% by mass or more and less than 100% by mass, and even more preferably 95% by mass or more and less than 100% by mass, based on the total mass of the chemical solution. The total content of aliphatic hydrocarbons and ester solvents is preferably 10 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 95 to 100% by mass, and particularly preferably 99 to 100% by mass, relative to the total mass of the organic solvent.

[0041] <Other solvents> The organic solvent may contain other solvents in addition to those listed above. Other solvents include, for example, ketone-based solvents, amide-based solvents, and ether-based solvents.

[0042] Organic solvents may be used individually or in combination of two or more types. The content of organic solvents is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on the total mass of the chemical solution. The upper limit is often less than 100% by mass, based on the total mass of the chemical solution. Methods for measuring the content of organic solvents include, for example, using GC (gas chromatography) and GC-MS (gas chromatography-mass spectrometry).

[0043] [Metal X] The chemical solution contains metal X. Metal X is at least one metal selected from the group consisting of Al, Fe, and Ni. Preferably, the chemical solution contains all of the metals Al, Fe, and Ni. The above-mentioned metal X may exist in an ionic state or in a 0-valent state in the chemical solution.

[0044] Metal X may be used alone or in combination of two or more types. The content of metal X is preferably 0.01 to 500 ppt by mass, more preferably 0.1 to 100 ppt by mass, and even more preferably 0.1 to 50 ppt by mass, relative to the total mass of the drug solution. If the drug solution contains two or more metals, it is preferable that the total content of the two or more metals falls within the above range. Furthermore, the content of at least one of Al, Fe, and Ni in metal X is preferably 0.1 to 100 ppt by mass relative to the total mass of the chemical solution.

[0045] The mass ratio of aromatic hydrocarbon content to metal X content (aromatic hydrocarbon content / metal X content) is 5.0 × 10⁻⁶ 4 ~2.0×10 10 Therefore, 3.0 × 10 5 ~1.0×10 9 Preferably, 3.0 × 10 5 ~2.5×10 8 This is preferable. Examples of known methods for measuring the content of metal X include ICP-MS (ICP mass spectrometry). Methods for adjusting the content of metal X include, for example, filtering using the above-mentioned filter, selecting raw materials with a low content of metal X as raw materials constituting various components, distilling under conditions that suppress contamination by lining the inside of the apparatus with Teflon®, and adding metal X or a compound containing metal X.

[0046] [Sulfur-containing compounds] The chemical solution may contain sulfur-containing compounds. Sulfur-containing compounds are not found in organic solvents. Examples of sulfur-containing compounds include thiol compounds, sulfide compounds, and thiophene compounds. Examples of thiol compounds include methanethiol, ethanethiol, 3-methyl-2-butene-1-thiol, 2-methyl-3-frantiol, furfurylthiol, 3-mercapto-3-methylbutylformate, phenylmercaptan, methylfurfurylmercaptan, ethyl 3-mercaptobutanoate, 3-mercapto-3-methylbutanol, and 4-mercapto-4-methyl-2-pentanone. Examples of sulfide compounds include dimethyl sulfide, dimethyl trisulfide, diisopropyl trisulfide, and bis(2-methyl-3-furyl) disulfide. Examples of thiophene compounds include alkylthiophene compounds, benzothiophene compounds, dibenzothiophene compounds, phenantrothiophene compounds, benzonaphthothiophene compounds, and thiophenesulfide compounds. As sulfur-containing compounds, sulfide compounds or thiophene compounds are preferred, and dimethyl sulfide or benzothiophene are more preferred.

[0047] Sulfur-containing compounds may be used individually or in combination of two or more. The sulfur-containing compound content is preferably 0.001 ppm by mass or more, and more preferably 0.01 ppm by mass or more, relative to the total mass of the drug solution. The upper limit is often less than 0.8% by mass, relative to the total mass of the drug solution, preferably 100 ppm by mass or less, and more preferably 5 ppm by mass or less. The mass ratio of aromatic hydrocarbons to sulfur-containing compounds (aromatic hydrocarbon content / sulfur-containing compound content) is preferably 1 or more, more preferably 100 or more, and even more preferably 200 or more. The upper limit is preferably 100,000 or less, more preferably 50,000, and even more preferably 10,000 or less.

[0048] C 10 H 14 Content, C 11 H 16 The content and C 10 H 12It is preferable that the content of each of these is greater than the content of the sulfur-containing compound. In other words, C 10 H 14 The content of is greater than the content of sulfur-containing compounds, C 11 H 16 The content of is greater than the content of sulfur-containing compounds and C 10 H 12 It is preferable that the content of is greater than the content of the sulfur-containing compound. C above 10 H 14 , the above C 11 H 16 , the above C 10 H 12 The sulfur-containing compounds mentioned above are as described above.

[0049] For example, the sulfur-containing compound content can be measured in accordance with JIS K2541-6:2013. Methods for adjusting the content of sulfur-containing compounds include, for example, selecting raw materials with a low content of sulfur-containing compounds as constituents of various components, distilling under conditions that suppress contamination by lining the apparatus with Teflon®, and adding sulfur-containing compounds.

[0050] [Alcohol compounds] The chemical solution may contain alcohol compounds. Alcohol compounds are not considered organic solvents, but rather organic impurities. In other words, the alcohol compound content is less than 8000 ppm by mass relative to the total mass of the chemical solution. Alcohol compounds are compounds that have an alcoholic hydroxyl group. The alcoholic hydroxyl group may be primary, secondary, or tertiary. Examples of alcohol compounds include well-known alcohol compounds. The number of carbon atoms in the alcohol compound is preferably 1 to 20, more preferably 1 to 5, and even more preferably 2 to 5. The alcohol compound preferably contains at least one selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, and 2-methyl-1-butanol, more preferably contains at least one selected from the group consisting of 1-butanol and methanol, and even more preferably contains 1-butanol.

[0051] Alcohol compounds may be used individually or in combination of two or more. The alcohol compound content is preferably 0.001 ppm by mass or more and less than 8000 ppm by mass, more preferably 0.1 to 5000 ppm by mass, even more preferably 1 to 500 ppm by mass, and particularly preferably 1 to 100 ppm by mass, relative to the total mass of the drug solution. The mass ratio of aromatic hydrocarbon content to alcohol compound content (aromatic hydrocarbon content / alcohol compound content) is 1.0 × 10⁻⁶ -4 ~1.0×10 5 A value of 0.001 to 200 is preferred, more preferably 0.01 to 100 is preferred. One example of a method for measuring the content of alcohol compounds is the method for measuring the content of the organic solvents mentioned above. Methods for adjusting the alcohol compound content include, for example, selecting raw materials with a low alcohol compound content as constituents of various components, distilling under conditions that suppress contamination by lining the apparatus with Teflon®, and adding alcohol compounds.

[0052] 〔water〕 The chemical solution preferably contains substantially no water. Specifically, the water content is preferably 1% by mass or less, more preferably 1 to 1000 ppm by mass, and even more preferably 20 to 1000 ppm by mass, relative to the total mass of the chemical solution. One example of a method for measuring the water content is the method for measuring the content of the organic solvent mentioned above. Methods for adjusting the water content include, for example, selecting raw materials with a low water content as components, distilling under conditions that suppress contamination by lining the equipment with Teflon®, and adding water.

[0053] [Other ingredients] The drug solution may contain other ingredients in addition to those listed above. Other components include, for example, well-known surfactants. The surfactant content is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and even more preferably 0.01 to 0.5% by mass, relative to the total mass of the drug solution.

[0054] <<Second Embodiment>> The second embodiment of the drug solution will be described in detail below. The second embodiment of the drug solution is preferably used as a rinse solution. Except for the points described in detail below, the second embodiment of the drug solution is the same as the first embodiment of the drug solution, and the preferred embodiment is also the same.

[0055] [Organic solvents] <Aliphatic hydrocarbons> The aliphatic hydrocarbon preferably contains an aliphatic hydrocarbon having 5 or more carbon atoms (preferably 15 or fewer carbon atoms), more preferably contains an aliphatic hydrocarbon having 10 or more carbon atoms (preferably 13 or fewer carbon atoms), even more preferably contains at least one selected from the group consisting of hexane, decane, undecane, dodecane, and methyldecane, particularly preferably contains at least one selected from the group consisting of decane, undecane, dodecane, and methyldecane, and most preferably contains undecane. The aliphatic hydrocarbon content is preferably 0.8% by mass or more and less than 100% by mass, more preferably 5 to 90% by mass, and even more preferably 10 to 60% by mass, based on the total mass of the drug solution. The aliphatic hydrocarbon content is preferably 0.8% to 100% by mass, more preferably 1 to 100% by mass, even more preferably 5 to 90% by mass, and particularly preferably 10 to 60% by mass, relative to the total mass of the organic solvent.

[0056] <Ester-based solvents> The content of the ester solvent is preferably 1% by mass or more and less than 100% by mass, more preferably 50 to 97% by mass, and even more preferably 50 to 92% by mass, based on the total mass of the chemical solution. The content of the ester solvent is preferably 1% by mass or more and less than 100% by mass, more preferably 50 to 97% by mass, and even more preferably 50 to 92% by mass, relative to the total mass of the organic solvent.

[0057] [Method for manufacturing chemical solutions] The method for manufacturing the drug solution is not particularly limited, and it can be manufactured by mixing the various components mentioned above. Furthermore, it is preferable to use high-purity grade products for each component. Furthermore, after mixing the various components, the mixture may be subjected to a purification process as needed. Purification processes include distillation and filtering.

[0058] The chemical solution is preferably used as a developer or rinse solution in the pattern formation method. The following pattern formation method is preferred.

[0059] [Pattern formation method] The pattern formation method includes a resist film formation step of forming a resist film using a photosensitive or radiation-sensitive resin composition (hereinafter also referred to as a "resist composition") described later, and The exposure process involves exposing the resist film, The process includes a developing step in which the exposed resist film is developed using a developer. The pattern formation method preferably includes the resist film formation step, the exposure step, and the development step in this order. The following describes each step in the pattern formation method in detail.

[0060] [Resist film formation process] The resist film formation process is a process of forming a resist film using a resist composition. One method for forming a resist film using a resist composition is to coat the resist composition onto a substrate. The resist composition will be described later. One method for applying a resist composition onto a substrate is to apply the resist composition onto a substrate (e.g., silicon) used in the manufacture of semiconductor devices such as integrated circuits, using equipment such as a spinner and a coater. As for the coating method, spin coating using a spinner is preferred. The preferred rotation speed for spin coating is 1000 to 3000 rpm.

[0061] The substrate coated with the resist composition may be dried to form a resist film. One drying method is, for example, heating. This heating may be carried out using means provided in a known exposure machine and / or a known developing machine, as well as a hot plate. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 30 to 800 seconds, and even more preferably 40 to 600 seconds. Heating may be performed once or two or more times.

[0062] The thickness of the resist film is preferably 10 to 90 nm, more preferably 10 to 65 nm, and even more preferably 15 to 50 nm, from the standpoint of forming a finer pattern with higher precision.

[0063] Furthermore, an underlayer (for example, an inorganic film, an organic film, or an anti-reflective film) may be formed between the substrate and the resist film. The resist composition for forming the undercoat preferably contains a known organic material or a known inorganic material. The thickness of the undercoat film is preferably 10 to 90 nm, more preferably 10 to 50 nm, and even more preferably 10 to 30 nm. Examples of resist compositions for forming the undercoat include AL412 (manufactured by Brewer Science) and the SHB series (e.g., SHB-A940, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0064] A topcoat may be formed on the side of the resist film opposite to the substrate using a topcoat resist composition. It is preferable that the topcoat resist composition is not mixed with the resist film and can be uniformly applied to the side of the resist film opposite to the substrate. The topcoat resist composition preferably contains a resin, additives, and a solvent. Examples of methods for forming a top coat include known methods for forming a top coat, specifically the method for forming a top coat described in paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543. As a method for forming the topcoat, it is preferable to form a topcoat containing the basic compound described in Japanese Patent Publication No. 2013-061648 on the side of the resist film opposite to the substrate. Examples of the basic compound include the basic compound described in International Publication No. 2017 / 002737. Furthermore, the top coat may also preferably contain a compound having at least one selected from the group consisting of -O-, -S-, a hydroxyl group, a thiol group, -CO-, and -COO-.

[0065] [Exposure process] The exposure process is the process of exposing the resist film to light. The exposure process is preferably a process of pattern exposure through a photomask. Examples of photomasks include well-known photomasks. Furthermore, the photomask may be in contact with the resist film. Examples of exposure light used to expose the resist film include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet (EUV), X-rays, and electron beams. The wavelength of the exposure light is preferably 250 nm or less, more preferably 220 nm or less, and even more preferably 1 to 200 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), X-rays, EUV (wavelength 13 nm), or electron beams are preferred, KrF excimer laser, ArF excimer laser, EUV, or electron beams are more preferred, and EUV or electron beams are even more preferred. The exposure level can be adjusted as needed to match the desired pattern shape. The exposure method in the exposure process may be immersion exposure. The exposure process may be performed once or two or more times.

[0066] After the exposure process and before the development process described later, a post-exposure bake (PEB) may be performed. The heating temperature for post-exposure baking is preferably 80-150°C, more preferably 80-140°C, and even more preferably 80-130°C. The heating time is preferably 10-1000 seconds, more preferably 10-180 seconds, and even more preferably 30-120 seconds. Post-exposure baking may be performed using means provided in known exposure and / or development machines, as well as a hot plate. Post-exposure baking may also be performed once or two or more times.

[0067] [Development process] The developing process is the process of developing the exposed resist film using a developer solution. Examples of the developer mentioned above include known developers, the above chemical solution is preferred, and the chemical solution of the first embodiment is more preferred. The above-mentioned chemical solution is as described above. As a developer other than the chemical solution mentioned above, at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents is preferred, with ester solvents being more preferred. Examples of ester solvents include butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, ethyl butyrate, ethyl isobutyrate, amyl formate, and isoamyl formate. Alternatively, the ester solvent may be any ester solvent that can be contained in the above-mentioned chemical solution.

[0068] Examples of development methods include well-known development methods. Specifically, these methods include immersing the exposed resist film in a tank filled with developer solution for a certain period of time (dip method), puddling the exposed resist film with developer solution due to surface tension and leaving it still for a certain period of time for development (paddle method), spraying the exposed resist film with developer solution (spray method), and continuously dispensing developer solution from a nozzle that dispenses developer solution at a constant speed while scanning a substrate having an exposed resist film that is rotating at a constant speed (dynamic dispensing method). Furthermore, after the developing process, a step may be performed to stop the development process using a solvent other than the developer. The development time is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds. The temperature of the developing solution during development is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0069] [Other processes] The pattern formation method may include other steps in addition to those described above. Other processes include, for example, a rinsing process.

[0070] <Rinsing process> The pattern formation method preferably includes a rinsing step after the developing step, in which the material is washed with a rinsing solution. Examples of the above-mentioned developer include known developers, the above-mentioned chemical solution is preferred, and the chemical solution of the second embodiment is more preferred. The above-mentioned chemical solution is as described above. As a developer other than the chemical solution mentioned above, at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents is preferred.

[0071] Examples of rinsing methods include the dipping method, the paddle method, the spray method, and the dynamic dispensing method described above in the development method. Furthermore, the pattern formation method may include a heating step (post-bake) after the rinsing step. The heating step removes any developer and rinsing solution remaining between and inside the patterns, and also improves the surface roughness of the patterns. The heating temperature in the above heating step is preferably 40 to 250°C, and more preferably 80 to 200°C. The heating time is preferably 10 to 180 seconds, and more preferably 30 to 120 seconds.

[0072] Furthermore, one preferred embodiment of the pattern formation method of the present invention is a resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, An exposure step of exposing the resist film, The exposed resist film is developed using a developing solution, A pattern forming method comprising a washing step of washing with a rinsing solution after the developing step, The above chemicals are used as the developing solution and rinsing solution. One embodiment is one in which the content of aliphatic hydrocarbons in the chemical solution used as a rinse solution relative to the organic solvent is greater than the content of aliphatic hydrocarbons in the chemical solution used as a developer relative to the organic solvent.

[0073] <Etching process> The pattern formation method may include an etching step in which the substrate is etched using the formed pattern as a mask. Examples of etching methods include known etching methods. Specifically, these include the methods described in the Proc. of SPIE Vol. 6924, 692420 (2008), Chapter 4 "Etching" of "Semiconductor Process Textbook, 4th Edition, Published in 2007 by SEMI Japan," and the methods described in Japanese Patent Publication No. 2009-267112.

[0074] <Purification process> The pattern formation method may include a purification step for purifying the resist composition, developer, rinse solution and / or other various components used in the pattern formation method (for example, a resist composition for forming an anti-reflective film and a resist composition for forming a top coat).

[0075] Examples of purification methods include known purification methods, with filtration using a filter or purification using an adsorbent being preferred. The pore size of the filter is preferably less than 100 nm, more preferably 10 nm or less, and even more preferably 5 nm or less. The lower limit is often 0.01 nm or more. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. The filter may also be composed of a composite material combining the above filter material and an ion exchange medium. The filter may be one that has been pre-cleaned with an organic solvent.

[0076] The filtration method using filters may involve connecting multiple types of filters in series or parallel. When using multiple types of filters, filters with different pore sizes and / or materials may be combined. The material to be purified may also be filtered once or two or more times. If filtering is performed two or more times, the filtration may be carried out in a circulating manner.

[0077] The method using an adsorbent may involve using only the adsorbent, or it may involve using a combination of the filter and the adsorbent. Examples of adsorbents include known adsorbents, specifically inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[0078] In the production of a resist composition, it is preferable to dissolve various components, such as resins that may be included in the resist composition, in an organic solvent, and then filter them in a circulating manner using multiple filters of different materials. Specifically, it is preferable to connect polyethylene filters with a pore size of 50 nm, nylon filters with a pore size of 10 nm, and polyethylene filters with a pore size of 3 nm in a sequential manner and circulate the filter 10 or more times. The pressure difference between each filter should preferably be small. Specifically, the pressure difference between each filter should preferably be 0.1 MPa or less, more preferably 0.05 MPa or less, and even more preferably 0.01 MPa or less. The lower limit is often greater than 0 MPa. Furthermore, it is preferable that the pressure difference between the filter and the filling nozzle be small. Specifically, it is preferable that it be 0.5 MPa or less, more preferably 0.2 MPa or less, and even more preferably 0.1 MPa or less. The lower limit is often greater than 0 MPa.

[0079] The resist composition is preferably filtered and then filled into a clean container. From the viewpoint of suppressing deterioration over time, it is further preferable that the resist composition filled into the container be stored under refrigeration. The time between the completion of filling the container with the resist composition and the start of refrigeration should be as short as possible. Specifically, it is preferably within 24 hours, more preferably within 16 hours, even more preferably within 12 hours, and particularly preferably within 10 hours. The refrigerated storage temperature is preferably 0 to 15°C, more preferably 0 to 10°C, and even more preferably 0 to 5°C.

[0080] The resist composition, developer, and other components are preferably free of impurities. Examples of impurities include metallic impurities. Specifically, these include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn. The impurity content of the resist composition is preferably 1 ppm or less by mass relative to the total mass of the resist composition, the impurity content of the developer is preferably 10 ppb or less by mass relative to the total mass of the developer, or the impurity content of each of the other components is preferably 10 ppt or less by mass relative to the total mass of the impurities of each of the other components (for example, the impurity content of the rinse solution is 1 ppm or less by mass relative to the total mass of the rinse solution, etc.), more preferably 10 ppb or less by mass, even more preferably 100 ppt or less by mass, particularly preferably 10 ppt or less by mass, and most preferably 1 ppt or less by mass. The lower limit is often 0 ppt or more by mass. Examples of methods for measuring impurities include known measurement methods such as ICP-MS (ICP mass spectrometry). Methods for reducing the content of the above-mentioned impurities include, for example, filtering using the above-mentioned filter, selecting raw materials with low impurity content as constituent materials for various materials, and distilling under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon®.

[0081] Liquids containing organic solvents, such as developing solutions and rinsing solutions, may contain conductive compounds to prevent malfunctions of chemical piping and various parts (e.g., filters, O-rings, and tubes) due to electrostatic charging and discharge. Examples of conductive compounds include methanol. From the viewpoint of maintaining developing performance or rinsing performance, the content of the conductive compound in the developer is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the developer, or the content of the conductive compound in the rinse solution is preferably 10% by mass or less, relative to the total mass of the rinse solution. The lower limit is often 0.01% by mass or more. Examples of materials used for chemical piping include stainless steel (SUS), or various materials coated with antistatic treated polyethylene, polypropylene, or fluororesin (e.g., polytetrafluoroethylene and perfluoroalkoxy resin). Examples of filters and O-rings include various materials coated with antistatic polyethylene, polypropylene, or fluororesin (e.g., polytetrafluoroethylene and perfluoroalkoxy resin).

[0082] The following embodiments of the drug solution are preferred. In the following embodiments, each term has the same meaning as the terms described above, and the same applies to the preferred embodiments.

[0083] <<First Embodiment>> A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, The exposure process involves exposing the resist film, A pattern formation method including a developing step of developing an exposed resist film using a developer, A chemical solution used as a developing solution.

[0084] <<Second Embodiment>> A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, The exposure process involves exposing the resist film, A developing step in which the exposed resist film is developed using butyl acetate, In a pattern forming method that includes a washing step of washing with a rinsing solution after the developing step, A chemical solution used as a rinse.

[0085] <<Third Embodiment>> A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, The exposure process involves exposing the resist film, The developed process involves developing the exposed resist film using a developer solution, In a pattern forming method that includes a washing step of washing with a rinsing solution after the developing step, A chemical solution used as a developing solution and rinsing solution.

[0086] In the third embodiment described above, the chemical solution used as the developer and the chemical solution used as the rinse solution may be the same or different, and it is preferable that they be different. The same chemical solution means that the types and amounts of components contained in the chemical solution are all the same. Furthermore, in the third embodiment described above, it is preferable that the content of aliphatic hydrocarbons (preferably undecane) in the chemical solution used as a rinse solution relative to the total mass of the organic solvent is greater than the content of aliphatic hydrocarbons (preferably undecane) in the chemical solution used as a developer relative to the total mass of the organic solvent. Specifically, the content of aliphatic hydrocarbons (preferably undecane) in the chemical solution used as a developer is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and even more preferably 5 to 15% by mass, relative to the total mass of the organic solvent. Furthermore, the content of aliphatic hydrocarbons (preferably undecane) in the chemical solution used as a rinse solution is preferably 5 to 100% by mass relative to the total mass of the organic solvent.

[0087] [Resist composition] The following details the components that may be included in the resist composition. The resist composition preferably contains a resin that decomposes and increases in polarity due to the action of an acid (hereinafter also referred to as "resin (A)") and a photoacid generator that generates acid upon irradiation with active light or radiation (hereinafter also referred to as "photoacid generator").

[0088] The resist composition is preferably a negative-type resist composition. Furthermore, the resist composition is also preferably a resist composition for organic solvent development. The resist composition is typically a chemically amplified resist composition.

[0089] [Resin (A)] The resist composition preferably contains resin (A). In a pattern formation method, typically, when a developer containing an organic solvent is used as the developer, a negative-type pattern is suitably formed. Resin (A) preferably contains groups that decompose and increase in polarity due to the action of an acid (hereinafter also referred to as "acid-decomposable groups"), and more preferably contains repeating units having acid-decomposable groups. In addition to the repeating units having acid-degradable groups described later, the repeating units having acid-degradable groups that include unsaturated bonds, described later, are also preferred as repeating units having acid-degradable groups that include unsaturated bonds.

[0090] <Repeating unit with acid-degradable group> (Repeating unit with acid-degradable group) The acid-degradable group is preferably a group that decomposes under the action of an acid to produce a polar group. The acid-degradable group preferably has a structure in which the polar group is protected by a leaving group that is removed by the action of an acid. In other words, the resin (A) preferably has repeating units having a group that decomposes by the action of an acid and generates a polar group. The resin having the above repeating units becomes more polar by the action of an acid, increasing its solubility in alkaline developers and decreasing its solubility in organic solvents. Preferred polar groups include alkali-soluble groups such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. The polar groups mentioned above are preferably carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups.

[0091] The resin (A) preferably contains at least one selected from the group consisting of a group in which a hydrogen atom of a carboxyl group is substituted with an acid-degradable group, a group in which a hydrogen atom of an alcoholic hydroxyl group is substituted with an acid-degradable group, and a group in which a hydrogen atom of a phenolic hydroxyl group is substituted with an acid-degradable group.

[0092] As a repeating unit having an acid-degradable group, the repeating unit represented by formula (A) is also preferred.

[0093] [ka]

[0094] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; and R2 represents a leaving group which is eliminated by the action of an acid which may have a fluorine atom or an iodine atom. However, at least one of L1, R1, and R2 has a fluorine atom or an iodine atom. L1 represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of divalent linking groups which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups which may have a fluorine atom or an iodine atom (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups formed by linking multiple of these. As L1, -CO-, arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom- is preferred, and -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom- is more preferred. A phenylene group is preferred as the arylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group 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 preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0095] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms. The total number of fluorine atoms and iodine atoms contained in an alkyl group having a fluorine atom or an iodine atom is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group described above may also contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0096] R2 represents a leaving group that is eliminated by the action of an acid and may contain a fluorine atom or an iodine atom. Examples of leaving groups that may contain a fluorine atom or an iodine atom include those represented by the above formulas (Y1) to (Y4) and that contain a fluorine atom or an iodine atom.

[0097] Examples of repeating units having acid-degradable groups include those described in paragraphs

[0031] to

[0063] of International Publication No. 2020-004306, the contents of which are incorporated herein by reference.

[0098] The content of repeating units having acid-degradable groups is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units of resin (A). The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0099] Examples of repeating units having acid-degradable groups include the following repeating units. In the formula, Xa1 represents H, CH3, CF3, or CH2OH. Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] (A repeating unit containing an unsaturated bond and an acid-degradable group) The resin (A) may have repeating units having acid-degradable groups containing unsaturated bonds. As a repeating unit having an acid-degradable group containing an unsaturated bond, the repeating unit represented by formula (B) is preferred.

[0106] [ka]

[0107] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or an optionally substituted divalent linking group. Ry1 to Ry3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry1 to Ry3 may bond to form a monocyclic or polycyclic (monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.).

[0108] Examples of alkyl groups that may have substituents, represented by Xb, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xb represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0109] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, with an aromatic ring group being preferred. L is preferably an -Rt- group, an -CO- group, an -COO-Rt-CO- group, or an -Rt-CO- group. Rt may have substituents such as a halogen atom, a hydroxyl group, or an alkoxy group. An aromatic ring group is preferred.

[0110] The alkyl groups Ry1 to Ry3 are preferably C1 to C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The cycloalkyl groups Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Ry1 to Ry3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl, naphthyl, and anthyl groups. A vinyl group is preferred as the alkenyl group for Ry1 to Ry3. An ethynyl group is preferred as the alkynyl group for Ry1 to Ry3. The cycloalkenyl groups of Ry1 to Ry3 are preferably structures in which a double bond is included in part of a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. The cycloalkyl group formed by the bonding of two Ry1-Ry3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Polycyclic cycloalkyl groups such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are also preferred. Monocyclic cycloalkyl groups having 5-6 carbon atoms are more preferred. The cycloalkyl or cycloalkenyl group formed by the bonding of two Ry1 to Ry3 may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group or -SO3- group, or a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl or cycloalkenyl groups, one or more of the ethylene groups constituting the cycloalkane or cycloalkene ring may be replaced by a vinylene group. In the repeating unit represented by formula (B), it is preferable that, for example, Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry2 and Rx3 are bonded to form the aforementioned cycloalkyl group or cycloalkenyl group.

[0111] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0112] The repeating units represented by formula (B) are preferably acid-degradable (meth)acrylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or acid-degradable styrene carboxylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (where Rt is an aromatic ring group)).

[0113] The content of repeating units having acid-degradable groups containing unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (A). The upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0114] Specific examples of repeating units having an acid-degradable group containing an unsaturated bond are shown below, but the present invention is not limited thereto. In the formula, Xb and L1 represent any of the substituents or linking groups described above, Ar represents an aromatic ring group, R represents a substituent such as a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR''' or -COOR''':R''' is an alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms), or carboxyl group, R' represents a linear or branched alkyl group, monocyclic or polycyclic cycloalkyl group, alkenyl group, alkynyl group, monocyclic or polycyclic aryl group, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group or -SO3- group, or a vinylidene group or a combination thereof, and n and m represent integers of 0 or more.

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] The resin (A) may contain repeating units other than those described above. For example, resin (A) may contain at least one repeating unit selected from the group consisting of the following group A and / or at least one repeating unit selected from the group consisting of the following group B. Group A: The group consisting of the following repeating units (20) to (29). (20) Repeating units having an acid group, as described later (21) Repeating units having a fluorine atom or an iodine atom, as described later (22) Repeating units having a lactone group, a sultone group or a carbonate group, as described later (23) Repeating units having a photoacid generating group, as described later (24) Repeating units represented by formula (V-1) or formula (V-2), as described later. (25) Repeating units represented by formula (A), as described later (26) Repeating units represented by formula (B), which will be described later (27) Repeating units represented by formula (C), as described later (28) Repeating units represented by formula (D), which will be described later (29) Repeating unit group B, which will be described later and is represented by formula (E): a group consisting of the following repeating units (30) to (32). (30) Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups, as described later. (31) Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition, as described later. (32) Repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group, as described later.

[0120] The resin (A) preferably has acidic groups, and more preferably contains repeating units having acidic groups, as will be described later. The definition of an acidic group will be explained later, along with preferred embodiments of the repeating units having acidic groups. When the resin (A) has acidic groups, the interaction between the resin (A) and the acid generated from the photoacid generator is improved. As a result, the diffusion of the acid is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular.

[0121] When the resist composition is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of group A. Furthermore, when the resist composition is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is preferable that resin (A) contains at least one of fluorine atoms and iodine atoms. If resin (A) contains both fluorine atoms and iodine atoms, resin (A) may have one repeating unit containing both fluorine atoms and iodine atoms, or resin (A) may contain two types of repeating units: repeating units containing fluorine atoms and repeating units containing iodine atoms. Furthermore, when the resist composition is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is also preferable that the resin (A) has repeating units having aromatic ring groups. When the resist composition is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of group B described above. Furthermore, when the resist composition is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not contain either fluorine atoms or silicon atoms. Furthermore, when the resist composition is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not have an aromatic ring group.

[0122] Resin (A) preferably has at least one selected from the group consisting of a lactone group, a carbonate group, a sultone group, and a ring group having a hydroxyl group. The lactone group, carbonate group, or sultone group will be described later. The ring group having a hydroxyl group is preferably an alicyclic group having a hydroxyl group, and specific examples include those exemplified in the repeating unit having an acid group, which will be described later.

[0123] <Repeating unit containing an acidic group> Resin (A) preferably has repeating units having acidic groups. As for the acid group, an acid group with a pKa of 13 or less is preferred. The pKa of the above acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (A) has acid groups with a pKa of 13 or less, the acid group content in resin (A) is often 0.2 to 6.0 mmol / g. Preferably, 0.8 to 6.0 mmol / g, more preferably 1.2 to 5.0 mmol / g, and even more preferably 1.6 to 4.0 mmol / g. If the acid group content is within the above range, development proceeds well, the resulting pattern shape is excellent, and the resolution is also excellent. Preferred acidic groups include, for example, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. Furthermore, one or more fluorine atoms (preferably 1 to 2) of the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group thus formed, -C(CF3)(OH)-CF2-, is also preferred. Alternatively, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acidic group is preferably different from the repeating unit having a structure in which a polar group is protected by a leaving group that is removed by the action of the acid described above, and from the repeating unit having a lactone group, sultone group, or carbonate group described later.

[0124] The repeating unit having an acidic group may also have a fluorine atom or an iodine atom. Examples of repeating units having an acidic group include the following:

[0125] [ka]

[0126] As a repeating unit having an acid group, the repeating unit represented by formula (Y) is preferred.

[0127] [ka]

[0128] In formula (Y), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. L represents a single bond or a divalent linking group having an oxygen atom. A single bond is preferred for L. R represents a halogen atom, alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, alkylcarbonyloxy group, alkylsulfonyloxy group, alkyloxycarbonyl group, or aryloxycarbonyl group. If there are multiple Rs, they may be the same or different. If there are multiple Rs, they may be bonded to each other to form a ring. A hydrogen atom is preferred as R. 'a' represents an integer between 1 and 3. b represents an integer between 0 and (5-a).

[0129] The following are examples of repeating units having an acid group. In the formulas, a represents 1 or 2.

[0130] [ka]

[0131] [ka]

[0132] [ka]

[0133] Furthermore, the repeating units described below are preferred as the repeating units mentioned above. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0134] [ka]

[0135] [ka]

[0136] The content of repeating units having acid groups is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units of resin (A). The upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units of resin (A).

[0137] <Repeating units containing fluorine, bromine, or iodine atoms> Resin (A) may have repeating units having fluorine atoms, bromine atoms, or iodine atoms, in addition to the <repeating units having acid-degradable groups> and <repeating units having acid groups> described above. Furthermore, it is preferable that the <repeating units having fluorine atoms, bromine atoms, or iodine atoms> referred to here are different from other types of repeating units belonging to group A, such as the <repeating units having lactone groups, sultone groups, or carbonate groups> and <repeating units having photoacid-generating groups> described later.

[0138] As a repeating unit having a fluorine atom, a bromine atom, or an iodine atom, the repeating unit represented by formula (C) is preferred.

[0139] [ka]

[0140] L5 represents a single bond or an ester group. R9 represents an alkyl group which may have a hydrogen atom or a fluorine atom, a bromine atom, or an iodine atom. R 10 This represents an alkyl group which may have a hydrogen atom, a fluorine atom, a bromine atom, or an iodine atom, a cycloalkyl group which may have a fluorine atom, a bromine atom, or an iodine atom, an aryl group which may have a fluorine atom, a bromine atom, or an iodine atom, or a group which is a combination thereof.

[0141] Examples of repeating units having fluorine or iodine atoms are shown below.

[0142] [ka]

[0143] The content of repeating units having fluorine atoms, bromine atoms, or iodine atoms is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total repeating units in resin (A). The upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, relative to the total repeating units in resin (A). As mentioned above, the repeating units having fluorine atoms, bromine atoms, or iodine atoms do not include <repeating units having acid-degradable groups> and <repeating units having acidic groups>. Therefore, the content of the repeating units having fluorine atoms, bromine atoms, or iodine atoms mentioned above also refers to the content of repeating units having fluorine atoms, bromine atoms, or iodine atoms excluding <repeating units having acid-degradable groups> and <repeating units having acidic groups>.

[0144] The total content of repeating units in resin (A) that contain at least one of fluorine atoms, bromine atoms, and iodine atoms is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, relative to the total repeating units of resin (A). The upper limit is, for example, 100 mol% or less, relative to the total repeating units of resin (A). Examples of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom include a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid-degradable group, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acidic group, and a repeating unit having a fluorine atom, a bromine atom, or an iodine atom.

[0145] <A repeating unit having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups> The resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups. First, we will explain repeating units having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups (hereinafter collectively referred to as "repeating units having lactone groups, sultone groups, or carbonate groups"). It is also preferable that the repeating units having a lactone group, a sultone group, or a carbonate group do not have acidic groups such as a hydroxyl group or a hexafluoropropanol group.

[0146] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. More preferably, the 5-7 membered ring lactone structure is fused with another ring structure in a way that forms a bicyclo or spiro structure, or the 5-7 membered ring sultone structure is fused with another ring structure in a way that forms a bicyclo or spiro structure. The resin (A) preferably has repeating units having lactone groups or sultone groups formed by removing one or more hydrogen atoms from the ring member atoms of a lactone structure represented by any of formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of formulas (SL1-1) to (SL1-3). Furthermore, lactone groups or sultone groups may be directly bonded to the main chain. For example, ring member atoms of lactone groups or sultone groups may constitute the main chain of resin (A).

[0147] [ka]

[0148] The lactone or sultone structure may have substituents (Rb2). Preferred substituents (Rb2) include C1-C8 alkyl groups, C4-C7 cycloalkyl groups, C1-C8 alkoxy groups, C1-C8 alkoxycarbonyl groups, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple Rb2 groups may be different, and the multiple Rb2 groups may bond to each other to form a ring.

[0149] An example of a repeating unit having a group containing a lactone structure represented by any of the formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the formulas (SL1-1) to (SL1-3) is the repeating unit represented by formula (AI).

[0150] [ka]

[0151] In formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of halogen atoms for Rb0 include fluorine, chlorine, bromine, and iodine. Rb0 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, a carboxyl group, or a divalent group combining these. A single bond or a linking group represented by -Ab1-CO2- is preferred. Ab1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, and a methylene group, ethylene group, cyclohexylene group, adamantylene group, or norbornylene group is preferred. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of the formulas (SL1-1) to (SL1-3).

[0152] If optical isomers exist for a repeating unit having a lactone group or a sultone group, either optical isomer may be used. Furthermore, one optical isomer may be used alone, or multiple optical isomers may be used in mixture form. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, and more preferably 95 or higher.

[0153] A cyclic carbonate ester group is preferred as the carbonate group. As a repeating unit having a cyclic carbonate ester group, the repeating unit represented by formula (A-1) is preferred.

[0154] [ka]

[0155] In formula (A-1), R A 1 This represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents a non-negative integer. R A 2 represents a substituent. If n is 2 or greater, there are multiple R A 2 These may be the same or different. A represents a single bond or a divalent linking group. Preferred divalent linking groups include alkylene groups, divalent linking groups having a monocyclic or polycyclic alicyclic hydrocarbon structure, ether groups, ester groups, carbonyl groups, carboxyl groups, or divalent groups that are combinations thereof. Z represents an atomic group that forms a monocyclic or polycyclic ring with the group represented by -O-CO-O- in the formula.

[0156] Examples of repeating units having a lactone group, a sultone group, or a carbonate group are shown below.

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] Next, we will describe repeating units having a hydroxyl group or a cyano group. The resin (A) may have repeating units 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. It is preferable that the repeating unit having a hydroxyl group or a cyano group does not have an acid-degradable group. Examples of repeating units having a hydroxyl group or a cyano group are those described in paragraphs

[0081] to

[0084] of Japanese Patent Application Publication No. 2014-98921.

[0161] Next, we will describe repeating units having alkali-soluble groups. The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bisulfonylimide groups, and aliphatic alcohols substituted at the α-position with an electron-withdrawing group (e.g., hexafluoroisopropanol group), with carboxyl groups being preferred. The inclusion of repeating units having alkali-soluble groups in resin (A) increases the resolution in contact hole applications. Examples of repeating units having alkali-soluble groups are those described in paragraphs

[0085] and

[0086] of Japanese Patent Application Publication No. 2014-98921.

[0162] The content of repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups is preferably 1 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in resin (A). The upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0163] <Repeating unit with photoacid-generating group> Resin (A) may also have repeating units other than those described above, which include a group that generates acid upon irradiation with active light or radiation (hereinafter also referred to as a "photoacid generating group"). Examples of repeating units having a photoacid-generating group are shown below.

[0164] [ka] JPEG0007869224000029.jpg4241

[0165] Examples of repeating units having a photoacid generating group include the repeating units described in paragraphs

[0094] to

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

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

[0166] The content of repeating units having photoacid generating groups is preferably 1 mol% or more, and more preferably 5 mol% or more, relative to the total repeating units in resin (A). The upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, relative to the total repeating units in resin (A).

[0167] <Repeating unit represented by formula (V-1) or formula (V-2)> The resin (A) may have repeating units represented by formula (V-1) or formula (V-2). The repeating units represented by formulas (V-1) and (V-2) are preferably different from the repeating units described above.

[0168] [ka]

[0169] In the formula, R6 and R7 each independently represent 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 having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group. Linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms are preferred as the alkyl group. n3 represents an integer between 0 and 6. n4 represents an integer between 0 and 4. X 4 This is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating unit described in paragraph

[0100] of International Publication No. 2018 / 193954.

[0170] <Repeating units to reduce the mobility of the main chain> Resin (A) is preferable to have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. The Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. However, excessively high Tg leads to a decrease in the dissolution rate in the developer, so the Tg is preferably 400°C or lower, and more preferably 350°C or lower. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of the repeating unit") is calculated by the following method. First, the Tg of each homopolymer consisting only of each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass percentage (%) of each repeating unit relative to the total number of repeating units in the polymer is calculated. Then, the Tg for each mass percentage is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the polymer's Tg (°C). The Bicerano method is described in *Prediction of polymer properties*, Marcel Dekker Inc, New York (1993). Furthermore, the calculation of Tg using the Bicerano method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0171] To increase the Tg of resin (A) (preferably, to make the Tg greater than 90°C), it is preferable to reduce the mobility of the main chain of resin (A). Methods for reducing the mobility of the main chain of resin (A) include the following (a) to (e): (a) introduction of bulky substituents to the main chain; (b) introduction of multiple substituents to the main chain; (c) introduction of substituents that induce interactions between resins (A) near the main chain; (d) formation of a main chain in a cyclic structure; (e) linkage of a cyclic structure to the main chain. Furthermore, it is preferable that resin (A) has repeating units in which the Tg of the homopolymer is 130°C or higher. In addition, the type of repeating unit in which the Tg of the homopolymer exhibits 130°C or higher may be any repeating unit in which the Tg of the homopolymer calculated by the Bicerano method is 130°C or higher. Depending on the type of functional group in the repeating unit represented by the following formulas (A) to (E), it corresponds to a repeating unit in which the Tg of the homopolymer exhibits 130°C or higher.

[0172] (Repeating unit represented by formula (A)) As an example of a specific achievement means of (a) above, a method of introducing a repeating unit represented by formula (A) into resin (A) can be mentioned.

[0173] [Chemical formula]

[0174] In formula (A), R A represents a group containing a polycyclic structure. R x represents a hydrogen atom, a methyl group or an ethyl group. The group containing a polycyclic structure is a group containing a plurality of ring structures, and the plurality of ring structures may be condensed or not condensed. Examples of the repeating unit represented by formula (A) include those described in paragraphs

[0107] to

[0119] of International Publication No. 2018 / 193954.

[0175] (Repeating unit represented by formula (B)) As an example of a specific achievement means of (b) above, a method of introducing a repeating unit represented by formula (B) into resin (A) can be mentioned.

[0176] [Chemical formula]

[0177] In formula (B), R b1 ~R b4 each independently represents a hydrogen atom or an organic group, and at least two or more of R b1 ~R b4 represent organic groups. Furthermore, if at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the types of other organic groups are not particularly limited. Furthermore, if none of the organic groups are directly linked to the main chain in the repeating unit, then at least two of the organic groups are substituents with three or more constituent atoms excluding hydrogen atoms. Examples of repeating units represented by formula (B) include those described in paragraphs

[0113] to

[0115] of International Publication No. 2018 / 193954.

[0178] (The repeating unit represented by formula (C)) One example of a specific means of achieving (c) above is to introduce repeating units represented by formula (C) into resin (A).

[0179] [ka]

[0180] In formula (C), R c1 ~R c4 Each of these independently represents a hydrogen atom or an organic group, and R c1 ~R c4 At least one of these groups contains hydrogen-bonding hydrogen atoms within three atoms of the main chain carbon. It is preferable to have hydrogen-bonding hydrogen atoms within two atoms (closer to the main chain) in order to induce interactions between the main chains of resin (A). Examples of repeating units represented by formula (C) include those described in paragraphs

[0119] to

[0121] of International Publication No. 2018 / 193954.

[0181] (The repeating unit represented by formula (D)) One example of a specific means of achieving (d) above is to introduce repeating units represented by formula (D) into resin (A).

[0182] [ka]

[0183] In formula (D), "cylic" represents a group that forms the main chain in a cyclic structure. The number of constituent atoms in the ring is not particularly limited. Examples of repeating units represented by formula (D) include those described in paragraphs

[0126] to

[0127] of International Publication No. 2018 / 193954.

[0184] (The repeating unit represented by formula (E)) One example of a specific means of achieving (e) above is to introduce repeating units represented by formula (E) into resin (A).

[0185] [ka]

[0186] In formula (E), Re independently represents either a hydrogen atom or an organic group. Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substitution mechanisms. A "cylic" is a cyclic group that contains carbon atoms in the main chain. There are no particular restrictions on the number of atoms that can be included in a cyclic group. Examples of repeating units represented by formula (E) include those described in paragraphs

[0131] to

[0133] of International Publication No. 2018 / 193954.

[0187] Resin (A) may have repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposition. This reduces the elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0188] <A repeating unit represented by formula (III) that does not contain either a hydroxyl group or a cyano group> Resin (A) may have repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group.

[0189] [ka]

[0190] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and lacking both a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group. Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of Japanese Patent Application Publication No. 2014-98921.

[0191] <Other repeating units> Furthermore, resin (A) may have repeating units other than those described above. For example, resin (A) may have repeating units selected from the group consisting of repeating units having an oxatian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. Examples of such repeating units are shown below.

[0192] [ka]

[0193] In addition to the repeating units described above, resin (A) may have various repeating units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0194] As for resin (A), (especially when the resist composition is used as an activated photosensitive or radiation-sensitive resin composition for ArF), it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. In this case, any of the following can be used: all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are composed of methacrylate repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units make up 50 mol% or less of the total repeating units.

[0195] Resin (A) can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight of resin (A), expressed as polystyrene equivalent, is preferably 30,000 or less, preferably 1,000 to 30,000, more preferably 3,000 to 30,000, and even more preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution) of resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The lower the degree of dispersion, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0196] In the resist composition, the content of resin (A) is preferably 40.0 to 99.9% by mass, and more preferably 60.0 to 90.0% by mass, based on the total solid content of the resist composition. Resin (A) may be used alone or in combination of multiple types.

[0197] [Photoacid generator]

[0198] The resist composition preferably contains a compound that generates acid upon irradiation with active light or radiation (photoacid generator). As a preferred embodiment of the photoacid generator, the following compound (I) or compound (II) can be mentioned. Hereinafter, compound (I) and compound (II) (hereinafter, "compound (I) and compound (II)" are also simply referred to as "photoacid generator PG1") will be described.

[0199] <Compound (I)> Compound (I) is a compound having one or more of the following structural moieties X and one or more of the following structural moieties Y, and generates an acid containing the following first acidic moiety derived from the following structural moiety X and the following second acidic moiety derived from the following structural moiety Y upon irradiation with actinic rays or radiation. Structural moiety X: Anionic moiety A1 - and cationic moiety M1 + which forms a first acidic moiety represented by HA1 upon irradiation with actinic rays or radiation Structural moiety Y: Anionic moiety A2 - and cationic moiety M2 + which forms a second acidic moiety represented by HA2 upon irradiation with actinic rays or radiation However, compound (I) satisfies the following condition I.

[0200] Condition I: In the above compound (I), the cationic moiety M1 in the above structural moiety X + and the cationic moiety M2 in the above structural moiety Y + are replaced with H + to form a compound PI, and the acid dissociation constant a1 derived from the acidic moiety represented by HA1 obtained by replacing the cationic moiety M1 in the above structural moiety X with H + with H + and the acid dissociation constant a2 derived from the acidic moiety represented by HA2 obtained by replacing the cationic moiety M2 in the above structural moiety Y with H + with H + such that the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0201] Hereinafter, condition I will be described more specifically. If compound (I) is a compound that generates an acid having, for example, one first acidic site derived from structural site X and one second acidic site derived from structural site Y, then compound PI falls under the category of "a compound having HA1 and HA2". To explain more specifically, when the acid dissociation constants a1 and a2 of compound PI are determined, if compound PI is "A1 - The pKa of the compound having HA2 is the acid dissociation constant a1, and the above "A1 - "A compound having HA2" is "A1 - and A2 - The pKa of a compound having the acid dissociation constant a2 is the pKa of the compound.

[0202] Furthermore, if compound (I) is a compound that generates an acid having, for example, two first acidic sites derived from structural site X and one second acidic site derived from structural site Y, then compound PI falls under the category of "a compound having two HA1 and one HA2". When the acid dissociation constant of such compound PI is determined, compound PI is "one A1 - The acid dissociation constant when a compound having one HA1 and one HA2 is formed, and the "one A1 - A compound having one HA1 and one HA2 is "two A1 - The acid dissociation constant when forming a compound having "and one HA2" corresponds to the above-mentioned acid dissociation constant a1. Also, "two A1 - A compound having one HA2 is a compound having two A1 - and A2 - The acid dissociation constant when a compound has the above-mentioned cation moiety M1 corresponds to the acid dissociation constant a2. In other words, as with such a compound PI, the above-mentioned cation moiety M1 in the above-mentioned structural moiety X + to H + If there are multiple acid dissociation constants originating from the acidic site represented by HA1, which is obtained by replacing with , the value of acid dissociation constant a2 is greater than the largest value of the multiple acid dissociation constants a1. -Let the acid dissociation constant when it becomes "a compound having one HA1 and one HA2" be aa, and "one A1" - When the compound having "one HA1 and one HA2" becomes "two A1s" - Let the acid dissociation constant when it becomes "a compound having one HA2" be ab. The relationship between aa and ab satisfies aa < ab.

[0203] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the measurement method of the acid dissociation constant described above. The above compound PI corresponds to the acid generated when the compound (I) is irradiated with actinic rays or radiation. When the compound (I) has two or more structural sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1s - and two or more of the above M1s + may be the same or different from each other. Also, in the compound (I), the above A1 - and the above A2 - , and the above M1 + and the above M2 + may be the same or different from each other, but it is preferable that the above A1 - and the above A2 - are different from each other.

[0204] In terms of the LWR performance of the formed pattern being more excellent, in the above compound PI, the difference 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 between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is, for example, 16 or less.

[0205] Also, in terms of the LWR performance of the formed pattern being more excellent, in the above compound PI, the acid dissociation constant a2 is, for example, 20 or less, and preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably -4.0 or more.

[0206] Furthermore, in terms of achieving superior LWR performance of the formed pattern, the acid dissociation constant a1 of the above compound PI 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 higher.

[0207] Anion part A1 - and anion part A2 - This refers to a structural site containing a negatively charged atom or group of atoms, and examples include structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. Anion site A1 - Preferably, it is possible to form an acidic site with a small acid dissociation constant, and it is preferably one of formulas (AA-1) to (AA-3). Also, anion site A2 - For example, Anion part A1 - It is preferable that an acidic site with a larger acid dissociation constant can be formed, and it is preferable that it be selected from any of formulas (BB-1) to (BB-6). In formulas (AA-1) to (AA-3) and (BB-1) to (BB-6) below, * represents the bond position. Also, R A R represents a monovalent organic group. A Examples of monovalent organic groups represented by include cyano groups, trifluoromethyl groups, and methanesulfonyl groups.

[0208] [ka]

[0209] [ka]

[0210] Also, cation site M1 + and cation site M2 + This is a structural site containing a positively charged atom or group of atoms, for example, a monovalent organic cation. Note that the organic cation is M in formula (Ia-1) described later. 11 + and M12 + Examples include organic cations similar to those represented by [the formula shown].

[0211] Specific examples of compound (I) include the compounds represented by formulas (Ia-1) to (Ia-5), which will be discussed later. Below, we will first discuss the compounds represented by formula (Ia-1). The compounds represented by formula (Ia-1) are as follows:

[0212] M 11 + A 11 - -L1-A 12 - M 12 + (Ia-1)

[0213] Compound (Ia-1) is HA when irradiated with active light or radiation. 11 -L1-A 12 It produces an acid represented by H.

[0214] In formula (Ia-1), M 11 + and M 12 + Each of these independently represents an organic cation. A 11 - and A 12 - Each of these independently represents a monovalent anionic functional group. L1 represents a divalent linking group. M 11 + and M 12 + These may be the same or different. A 11 - and A 12 - These may be the same or different, but it is preferable that they are different from each other. However, in the above equation (Ia-1), M 11 + and M 12+ The organic cation represented by H + The compound PIa(HA) is formed by replacing it with PIa(HA) 11 -L1-A 12 In H), A 12 The acid dissociation constant a2, which originates from the acidic site represented by H, is HA 11 It is greater than the acid dissociation constant a1 derived from the acidic site represented by (Ia-1). The preferred values ​​for the acid dissociation constants a1 and a2 are as described above. Furthermore, the acid generated from compound PIa and the acid generated from the compound represented by formula (Ia-1) upon irradiation with active light or radiation are the same. Also, M 11 + M 12 + , A 11 - , A 12 - And at least one of L1 may have an acid-degradable group as a substituent.

[0215] In formula (Ia-1), M 11 + and M 12 + The organic cation represented by is described below.

[0216] A 11 - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - It means a monovalent group that includes A. 12 - The monovalent anionic functional group represented by is the anionic moiety A2 mentioned above. - It refers to a monovalent group that includes [a specific component]. A 11 - and A 12 -The monovalent anionic functional group represented by is preferably a monovalent anionic functional group containing any of the anionic moieties of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) described above, and more preferably a monovalent anionic functional group selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7). 11 - The monovalent anionic functional group represented by is preferably a monovalent anionic functional group represented by any of the formulas (AX-1) to (AX-3). Also, A 12 - As the monovalent anionic functional group represented by , a monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-7) is preferred, and a monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-6) is more preferred.

[0217] [ka]

[0218] In formulas (AX-1) to (AX-3), R A1 and R A2 Each of these independently represents a monovalent organic group. * represents a bond position.

[0219] R A1 Examples of monovalent organic groups represented by include cyano groups, trifluoromethyl groups, and methanesulfonyl groups.

[0220] R A2 The monovalent organic group represented by is preferably a linear, branched, or cyclic alkyl group or aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group described above may have substituents. Preferably, the substituents are fluorine atoms or cyano groups, and more preferably fluorine atoms. If the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0221] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents are fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), or cyano groups, with fluorine atoms, iodine atoms, or perfluoroalkyl groups being more preferred.

[0222] In equations (BX-1) to (BX-4) and (BX-6), R B represents a monovalent organic group. * represents a bond position. R B The monovalent organic group represented by is preferably a linear, branched, or cyclic alkyl group or aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group described above may have substituents. Preferably, the substituent is a fluorine atom or a cyano group, and more preferably a fluorine atom. If the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. In addition, the carbon atoms that become the bonding positions in the alkyl group (for example, in the cases of formulas (BX-1) and (BX-4), the carbon atoms directly bonded to the -CO- explicitly stated in the alkyl group formula are the relevant carbon atoms; in the cases of formulas (BX-2) and (BX-3), the carbon atoms directly bonded to the -SO2- explicitly stated in the alkyl group formula are the relevant carbon atoms; and in the case of formula (BX-6), the carbon atoms directly bonded to the -N explicitly stated in the alkyl group formula are the relevant carbon atoms) - - This refers to the carbon atom directly bonded to it. ) If it has substituents, it is also preferable that the substituents are other than fluorine atoms or cyano groups. Furthermore, the alkyl group may have carbon atoms substituted with carbonyl carbons.

[0223] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents include fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, preferably having 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms), cyano groups, alkyl groups (for example, preferably having 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms), alkoxy groups (for example, preferably having 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms), or alkoxycarbonyl groups (for example, preferably having 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms), with fluorine atoms, iodine atoms, perfluoroalkyl groups, alkyl groups, alkoxy groups, or alkoxycarbonyl groups being more preferred.

[0224] In formula (I), the divalent linking group represented by L1 may be -CO-, -NR-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene group (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), or divalent aliphatic heterocyclic group (having at least one N, O, S or Se atom in the ring structure). Examples of divalent linking groups include 5-10 membered rings, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings, divalent aromatic heterocyclic groups (5-10 membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings), divalent aromatic hydrocarbon ring groups (6-10 membered rings, and even more preferably 6 membered rings), and groups combining these. The above R can be a hydrogen atom or a monovalent organic group. As a monovalent organic group, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred. Furthermore, the alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0225] Among the divalent linking groups represented by L1, the divalent linking group represented by formula (L1) is preferred.

[0226] [ka]

[0227] In formula (L1), L 111 This represents a single bond or a divalent linking group. L 111 Examples of divalent linking groups represented by include -CO-, -NH-, -O-, -SO-, -SO2-, optionally substituted alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), optionally substituted cycloalkylene groups (preferably having 3 to 15 carbon atoms), optionally substituted arylene groups (preferably having 6 to 10 carbon atoms), and divalent linking groups formed by combinations thereof. Examples of substituents include halogen atoms. p represents an integer between 0 and 3, preferably an integer between 1 and 3. Each Xf1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Each Xf2 independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and more preferably a fluorine atom or a perfluoroalkyl group. Xf1 and Xf2 are preferably, independently, a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. In particular, it is even more preferable that both Xf1 and Xf2 are fluorine atoms. * indicates the connection position. If L1 in formula (Ia-1) represents a divalent linking group represented by formula (L1), then L in formula (L1) 111The side joint (*) is A in equation (Ia-1). 12 - It is preferable that it be bonded with.

[0228] In formula (I), M 11 + and M 12 + As an organic cation represented by the above-mentioned <polarity-reducing groups, interacting groups and polar groups>, the M in the group represented by formula (O1) as described in the section on onium bases, which are a form of polarity-reducing group A + Examples of organic cations similar to those represented by [formula] are available, and the preferred embodiments are also the same.

[0229] Below M 11 + and M 12 + The present invention provides specific examples of organic cations represented by [formula], but is not limited thereto.

[0230] [ka]

[0231] [ka] JPEG0007869224000044.jpg95141

[0232] Next, we will explain equations (Ia-2) to (Ia-4).

[0233] [ka]

[0234] In equation (Ia-2), A 21a - and A 21b - Each of these independently represents a monovalent anionic functional group. Here, A 21a - and A 21b -The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - It means a monovalent group containing A. 21a - and A 21b - Examples of monovalent anionic functional groups represented by the above formulas (AX-1) to (AX-3) include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 22 - represents a divalent anionic functional group. Here, A 22 - The divalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a divalent group that includes A. 22 - Examples of divalent anionic functional groups represented by the formulas (BX-8) to (BX-11) shown below include the divalent anionic functional groups represented by the formulas (BX-8) to (BX-11).

[0235] [ka]

[0236] M 21a + M 21b + and M 22 + Each of these independently represents an organic cation. 21a + M 21b + and M 22 + The organic cation represented by the above M1 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 21 and L 22 Each of these independently represents a divalent organic group.

[0237] Furthermore, in the above equation (Ia-2), M 21a + M 21b + and M 22 +The organic cation represented by H + In compound PIa-2, which is obtained by substituting A, 22 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 21a Acid dissociation constants a1-1 and A derived from H 21b It is greater than the acid dissociation constant a1-2, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-1 and a1-2 correspond to the acid dissociation constant a1 mentioned above. Note A 21a - and A 21b - They may be the same or different from each other. Also, M 21a + M 21b + and M 22 + They may be the same or different from one another. Also, M 21a + M 21b + M 22 + , A 21a - , A 21b - , A 22 - , L 21 and L 22 At least one of these may have an acid-degradable group as a substituent.

[0238] In equation (Ia-3), A 31a - and A 32 - Each of these independently represents a monovalent anionic functional group. 31a - The definition of a monovalent anionic functional group represented by is A in formula (Ia-2) above. 21a - and A 21b - This is synonymous with the same thing, and the preferred embodiment is also the same. A 32 - The monovalent anionic functional group represented by is the anionic moiety A2 described above. -It means a monovalent group containing A. 32 - Examples of monovalent anionic functional groups represented by the above formulas (BX-1) to (BX-7) include monovalent anionic functional groups selected from the group consisting of the above formulas. A 31b - represents a divalent anionic functional group. Here, A 31b - The divalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a divalent group that includes A. 31b - Examples of divalent anionic functional groups represented by the formula (AX-4) shown below include the divalent anionic functional group represented by the formula (AX-4).

[0239] [ka]

[0240] M 31a + M 31b + and M 32 + Each of these independently represents a monovalent organic cation. 31a + M 31b + and M 32 + The organic cation represented by the above M1 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 31 and L 32 Each of these independently represents a divalent organic group.

[0241] Furthermore, in the above equation (Ia-3), M 31a + M 31b + and M 32 + The organic cation represented by H + In compound PIa-3, which is obtained by substituting A, 32The acid dissociation constant a2, which originates from the acidic site represented by H, is A 31a Acid dissociation constants a1-3 and A, derived from the acidic site represented by H. 31b It is larger than the acid dissociation constant a1-4, which originates from the acidic site represented by H. Note that acid dissociation constants a1-3 and a1-4 correspond to the acid dissociation constant a1 mentioned above. Note A 31a - and A 32 - They may be the same or different from each other. Also, M 31a + M 31b + and M 32 + They may be the same or different from one another. Also, M 31a + M 31b + M 32 + , A 31a - , A 31b - , A 32 - , L 31 and L 32 At least one of these may have an acid-degradable group as a substituent.

[0242] In equation (Ia-4), A 41a - , A 41b - and A 42 - Each of these independently represents a monovalent anionic functional group. 41a - and A 41b - The definition of a monovalent anionic functional group represented by is A in formula (Ia-2) above. 21a - and A 21b - It is synonymous with A. 42 - The definition of a monovalent anionic functional group represented by is A in formula (Ia-3) above. 32 -This is synonymous with the same thing, and the preferred embodiment is also the same. M 41a + M 41b + and M 42 + Each of these independently represents an organic cation. L 41 This represents a trivalent organic group.

[0243] Furthermore, in the above equation (Ia-4), M 41a + M 41b + and M 42 + The organic cation represented by H + In compound PIa-4, which is obtained by substituting A, 42 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 41a Acid dissociation constants a1-5 and A, derived from the acidic site represented by H. 41b It is larger than the acid dissociation constant a1-6 derived from the acidic site represented by H. Note that acid dissociation constants a1-5 and a1-6 correspond to the acid dissociation constant a1 mentioned above. Note A 41a - , A 41b - and A 42 - They may be the same or different from each other. Also, M 41a + M 41b + and M 42 + They may be the same or different from one another. Also, M 41a + M 41b + M 42 + , A 41a - , A 41b - , A 42 - and L 41 At least one of these may have an acid-degradable group as a substituent.

[0244] L in equation (Ia-2) 21 and L 22 , and also L in equation (Ia-3) 31 and L 32 Examples of divalent organic groups represented by include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure; more preferably 5 to 7-membered rings; even more preferably 5 to 6-membered rings), divalent aromatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure; more preferably 5 to 7-membered rings; even more preferably 5 to 6-membered rings), divalent aromatic hydrocarbon ring groups (preferably 6 to 10-membered rings; even more preferably 6-membered rings), and divalent organic groups formed by combining these. The above R can be a hydrogen atom or a monovalent organic group. As a monovalent organic group, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred. Furthermore, the alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0245] L in equation (Ia-2) 21 and L 22 , and also L in equation (Ia-3) 31 and L 32 The divalent organic group represented by is preferably, for example, the divalent organic group represented by formula (L2).

[0246] [ka]

[0247] In equation (L2), q represents an integer between 1 and 3. * indicates the joining position. Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. In particular, it is even more preferable that both Xf are fluorine atoms.

[0248] L A This represents a single bond or a divalent linking group. L A Examples of divalent linking groups represented by include -CO-, -O-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring groups (preferably 6 to 10-membered rings, more preferably 6-membered rings), and divalent linking groups formed by combining these. Furthermore, the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0249] Examples of divalent organic groups represented by formula (L2) include *-CF2-*, *-CF2-CF2-*, *-CF2-CF2-CF2-*, *-Ph-O-SO2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, *-Ph-O-SO2-CF2-CF2-CF2-*, and *-Ph-OCO-CF2-*. Herein, Ph is a phenylene group which may have substituents, and is preferably a 1,4-phenylene group. Preferred substituents are alkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), alkoxy groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), or alkoxycarbonyl groups (for example, those having 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are more preferred). L in equation (Ia-2) 21 and L 22 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-2). 22 - It is preferable that it be bonded with. Also, L in equation (Ia-3) 32 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-3). 32 - It is preferable that it be bonded with.

[0250] L in equation (Ia-4) 41 Examples of trivalent organic groups represented by this formula include the trivalent organic group represented by formula (L3).

[0251] [ka]

[0252] In formula (L3), L B * represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group. * represents the bond position.

[0253] The hydrocarbon ring group may be an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The number of carbon atoms in the hydrocarbon ring group is preferably 6 to 18, more preferably 6 to 14. The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group. The heterocyclic ring is preferably a 5 to 10-membered ring having at least one N, O, S, or Se atom in its ring structure, more preferably a 5 to 7-membered ring, and even more preferably a 5 to 6-membered ring. L B A trivalent hydrocarbon ring group is preferred, and a benzene ring group or an adamantane ring group is more preferred. The benzene ring group or adamantane ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0254] Also, in equation (L3), L B1 ~L B3 Each of these independently represents a single bond or a divalent linking group. B1 ~L B3 Examples of divalent linking groups represented by include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure; more preferably 5 to 7-membered rings; even more preferably 5 to 6-membered rings), divalent aromatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure; more preferably 5 to 7-membered rings; even more preferably 5 to 6-membered rings), divalent aromatic hydrocarbon ring groups (preferably 6 to 10-membered rings; even more preferably 6-membered rings), and groups combining these. The above R can be a hydrogen atom or a monovalent organic group. As a monovalent organic group, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred. Furthermore, the alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms). L B1 ~L B3 Preferred divalent linking groups represented by the above are -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene groups which may have substituents, and divalent linking groups formed by combining them.

[0255] L B1 ~L B3 Among the divalent linking groups represented by , the divalent linking group represented by formula (L3-1) is more preferable.

[0256] [ka]

[0257] In formula (L3-1), L B11 This represents a single bond or a divalent linking group. L B11 Examples of divalent linking groups represented by include -CO-, -O-, -SO-, -SO2-, alkylene groups which may have substituents (preferably having 1 to 6 carbon atoms; which may be linear or branched), and divalent linking groups formed by combining these. Examples of substituents include halogen atoms. r represents an integer between 1 and 3. Xf is synonymous with Xf in equation (L2) described above, and the preferred embodiment is the same. * indicates the connection position.

[0258] L B1 ~L B3 Examples of divalent linking groups represented by include *-O-*, *-O-SO2-CF2-*, *-O-SO2-CF2-CF2-*, *-O-SO2-CF2-CF2-CF2-*, and *-COO-CH2-CH2-*. L in equation (Ia-4) 41 It contains a divalent linking group represented by formula (L3-1), and the divalent linking group represented by formula (L3-1) and A 42 - When and bond, the bond on the carbon atom side (*) explicitly shown in formula (L3-1) is A in formula (Ia-4). 42 - It is preferable that it be bonded with. Also, L in equation (Ia-4) 41 It contains a divalent linking group represented by formula (L3-1), and the divalent linking group represented by formula (L3-1) and A 41a - and A 41b - When and bond, the bond on the carbon atom side (*) explicitly shown in formula (L3-1) is A in formula (Ia-4). 41a - and A 41b - Combining with this is also preferable.

[0259] Next, let's explain equation (Ia-5).

[0260] [ka]

[0261] In equation (Ia-5), A 51a - , A 51b - and A 51c - Each of these independently represents a monovalent anionic functional group. Here, A 51a - , A 51b - and A 51c - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - It means a monovalent group containing A. 51a - , A 51b - and A 51c -Examples of monovalent anionic functional groups represented by the above formulas (AX-1) to (AX-3) include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 52a - and A 52b - represents a divalent anionic functional group. Here, A 52a - and A 52b - The divalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a divalent group that includes A. 52a - and A 52b - Examples of divalent anionic functional groups represented by the above formulas (BX-8) to (BX-11) include divalent anionic functional groups selected from the group consisting of the above formulas.

[0262] M 51a + M 51b + M 51c + M 52a + and M 52b + Each of these independently represents an organic cation. 51a + M 51b + M 51c + M 52a + and M 52b + The organic cation represented by the above M1 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 51 and L 53 Each of these independently represents a divalent organic group. 51 and L 53 As a divalent organic group represented by the above formula (Ia-2), L 21 and L 22 This is synonymous with the same as the preferred embodiment. Note that L in formula (Ia-5) 51When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-5). 52a - It is also preferable to combine with L in equation (Ia-5). 53 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-5). 52b - Combining with this is also preferable. L 52 L represents a trivalent organic group. 52 As a trivalent organic group represented by the above formula (Ia-4), L 41 This is synonymous with the same as the preferred embodiment. Note that L in formula (Ia-5) 52 It contains a divalent linking group represented by formula (L3-1), and the divalent linking group represented by formula (L3-1) and A 51c - When and bond, the bond on the carbon atom side (*) explicitly shown in formula (L3-1) is A in formula (Ia-5). 51c - Combining with this is also preferable.

[0263] Furthermore, in the above equation (Ia-5), M 51a + M 51b + M 51c + M 52a + and M 52b + The organic cation represented by H + In compound PIa-5, which is obtained by substituting A, 52a Acid dissociation constants a2-1 and A, which originate from the acidic site represented by H. 52b The acid dissociation constant a2-2, which originates from the acidic site represented by H, is A 51a Acid dissociation constants a1-1 and A derived from H. 51b Acid dissociation constants a1-2 and A, derived from the acidic site represented by H. 51cThis is greater than the acid dissociation constant a1-3 derived from the acidic site represented by H. Note that acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1 mentioned above, and acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 mentioned above. Note A 51a - , A 51b - and A 51c - They may be the same or different from each other. Also, A 52a - and A 52b - They may be the same or different from each other. Also, M 51a + M 51b + M 51c + M 52a + and M 52b + They may be the same or different from one another. Also, M 51b + M 51c + M 52a + M 52b + , A 51a - , A 51b - , A 51c - , L 51 , L 52 and L 53 At least one of these may have an acid-degradable group as a substituent.

[0264] <Compound (II)> Compound (II) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, which generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural sites Z upon irradiation with active light or radiation. Structural site Z: A nonionic site capable of neutralizing acids.

[0265] Definition of structural site X in compound (II), and A1 - and M1 + The definition is the definition of structural site X in compound (I) described above, and A1 - and M1 + This is synonymous with the definition of [the specified term], and the preferred embodiment is also the same.

[0266] In the above compound (II), the above cation moiety M1 in the above structural moiety X + to H + In compound PII obtained by replacing with the above structural site X, the above cation site M1 + to H + The preferred range for the acid dissociation constant a1 derived from the acidic moiety represented by HA1, which is obtained by replacing it with the above compound PI, is the same as the acid dissociation constant a1 in the above compound PI. Furthermore, if compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the above structural site X and the above structural site Z, then compound PII falls under the category of "a compound having two HA1s". When the acid dissociation constant of this compound PII is determined, compound PII is "a compound having one A1 - The acid dissociation constant and "one A1" when it becomes a compound having one HA1 - A compound having one HA1 is a compound having two A1 - The acid dissociation constant when a compound becomes "a compound having " corresponds to the acid dissociation constant a1.

[0267] The acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above. The above compound PII refers to the acid generated when compound (II) is irradiated with active light or radiation. Note that the two or more structural parts X described above may be the same or different. Also, two or more of the above A1 - and two or more of the above M1 + These may be the same or different.

[0268] The nonionic site in structural site Z that can neutralize the acid is preferably, for example, a site containing a group that can electrostatically interact with a proton or a functional group that has electrons. Examples of functional groups having groups or electrons that can electrostatically interact with protons include functional groups having a macrocyclic structure such as cyclic polyethers, or functional groups having a nitrogen atom with a lone pair of electrons that does not contribute to π-conjugation. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having the substructure shown in the formula.

[0269] [ka]

[0270] Examples of functional group substructures having a group or electron that can electrostatically interact with a proton include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, with primary to tertiary amine structures being preferred.

[0271] Examples of compound (II) include the compounds represented by formulas (IIa-1) and (IIa-2).

[0272] [ka]

[0273] In the above equation (IIa-1), A 61a - and A 61b - These are A in equation (Ia-1) mentioned above. 11 - It is synonymous with the same as the preferred embodiment. Also, M 61a + and M 61b + These are M in equation (Ia-1) described above. 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. In the above equation (IIa-1), L61 and L 62 These terms are equivalent to L1 in the above-mentioned formula (Ia-1), and the preferred embodiments are the same. Note that L in equation (IIa-1) 61 When represents a divalent linking group represented by formula (L1), the L in formula (L1) 111 It is preferable that the bond (*) on the side is bonded to the nitrogen atom explicitly shown in formula (IIa-1). Also, L in formula (IIa-1) 62 When represents a divalent linking group represented by formula (L1), the L in formula (L1) 111 It is preferable that the bond (*) on the side is bonded to the nitrogen atom explicitly shown in formula (IIa-1).

[0274] In formula (IIa-1), R 2X R represents a monovalent organic group. 2X Examples of monovalent organic groups represented by include alkyl groups (preferably having 1 to 10 carbon atoms; may be linear or branched), cycloalkyl groups (preferably having 3 to 15 carbon atoms), or alkenyl groups (preferably having 2 to 6 carbon atoms), in which -CH2- may be substituted with one or more selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-. Furthermore, the alkylene group, the cycloalkylene group, and the alkenylene group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0275] Furthermore, in the above equation (IIa-1), M 61a + and M 61b + The organic cation represented by H + In compound PIIa-1, which is obtained by substituting A, 61a Acid dissociation constants a1-7 and A, derived from the acidic site represented by H. 61b The acid dissociation constants a1-8, derived from the acidic site represented by H, correspond to the acid dissociation constant a1 mentioned above. Furthermore, in the above compound (IIa-1), the above cation site M in the above structural site X. 61a+ and M 61b + to H + Compound PIIa-1, which is obtained by replacing HA, 61a -L 61 -N(R 2X )-L 62 -A 61b H is the corresponding element. Furthermore, compound PIIa-1 and the acid generated from the compound represented by formula (IIa-1) upon irradiation with active light or radiation are the same. Also, M 61a + M 61b + , A 61a - , A 61b - , L 61 , L 62 and R 2X At least one of these may have an acid-degradable group as a substituent.

[0276] In the above equation (IIa-2), A 71a - , A 71b - and A 71c - These are A in equation (Ia-1) mentioned above. 11 - It is synonymous with the same as the preferred embodiment. Also, M 71a + M 71b + and M 71c These are M in equation (Ia-1) described above. 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. In the above equation (IIa-2), L 71 , L 72 and L 73 These terms are equivalent to L1 in the above-mentioned formula (Ia-1), and the preferred embodiments are the same. Note that L in equation (IIa-2) 71 When represents a divalent linking group represented by formula (L1), the L in formula (L1) 111It is preferable that the bond (*) on the side is bonded to the nitrogen atom explicitly shown in formula (IIa-2). Also, L in formula (IIa-2) 72 When represents a divalent linking group represented by formula (L1), the L in formula (L1) 111 It is preferable that the bond (*) on the side is bonded to the nitrogen atom explicitly shown in formula (IIa-2). Also, L in formula (IIa-2) 73 When represents a divalent linking group represented by formula (L1), the L in formula (L1) 111 It is preferable that the bond (*) on the side is bonded to the nitrogen atom explicitly shown in formula (IIa-2).

[0277] Furthermore, in the above equation (IIa-2), M 71a + M 71b + and M 71c + The organic cation represented by H + In compound PIIa-2, which is obtained by substituting A, 71a Acid dissociation constants a1-9 and A, derived from the acidic site represented by H. 71b Acid dissociation constants a1-10 and A, derived from the acidic site represented by H. 71c The acid dissociation constants a1-11, derived from the acidic site represented by H, correspond to the acid dissociation constant a1 mentioned above. Furthermore, in the above compound (IIa-2), the above cation site M in the above structural site X. 71a + M 71b + and M 71c + Compound PIIa-2, which is obtained by replacing HA, 71a -L 71 -N(L 73 -A 71c H)-L 72 -A 71b H is the corresponding element. Furthermore, compound PIIa-2 and the acid generated from the compound represented by formula (IIa-2) upon irradiation with active light or radiation are the same. Also, M 71a + M 71b + M 71c+ , A 71a - , A 71b - , A 71c - , L 71 , L 72 and L 73 At least one of these may have an acid-degradable group as a substituent.

[0278] The molecular weight of the photoacid generator PG1 is preferably 100 to 10000, more preferably 100 to 2500, and even more preferably 100 to 1500.

[0279] <Other photoacid generators> Another preferred embodiment of the photoacid generator is a photoacid generator other than the aforementioned photoacid generator PG1 (hereinafter also referred to as "photoacid generator PG2").

[0280] For example, the photoacid generator PG2 is "M + X - Examples include compounds represented by '' (onium salt compounds), and it is preferable that these compounds generate organic acids upon exposure. Examples of the above-mentioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methidic acids.

[0281] "M + X - In the compound represented by ", M + This represents an organic cation. The above organic cation is the M in the group represented by formula (O1), which was described as an onium base, a form of polarity-reducing group, in the section above on <polarity-reducing groups, interacting groups, and polar groups>. A +Examples of organic cations similar to those represented by are given, and specifically, cations represented by formula (ZaI) (cation(ZaI)) or cations represented by formula (ZaII) (cation(ZaII)) are preferred. "M + X - In the compound represented by ", X - This represents an organic anion. The above organic anion is the X in the group represented by formula (O2), which was described as an onium base, a form of polarity-reducing group, in the section above on <polarity-reducing groups, interacting groups, and polar groups>. B - Examples include organic cations similar to those represented by [the formula shown].

[0282] As the photoacid generator PG2, it is also preferable to use the photoacid generators disclosed in paragraphs

[0135] to

[0171] of International Publication No. 2018 / 193954, paragraphs

[0077] to

[0116] of International Publication No. 2020 / 066824, and paragraphs

[0018] to

[0075] and

[0334] to

[0335] of International Publication No. 2017 / 154345.

[0283] The molecular weight of the photoacid generator PG2 is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.

[0284] If the resist composition contains a photoacid generator, its content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5.0% by mass or more, relative to the total solid content of the resist composition. Furthermore, the above content is preferably 40.0% by mass or less, and more preferably 30.0% by mass or less. The photoacid generator may be used alone or in combination of two or more types. When using two or more types, it is preferable that their total content is within the range of the preferred content described above.

[0285] [Acid diffusion control agent] The resist composition may contain an acid diffusion control agent. Acid diffusion control agents act as quenchers that trap acids generated from photoacid generators during exposure, thereby suppressing the reaction of the resin in unexposed areas due to excess generated acid. Examples of acid diffusion control agents that can be used include basic compounds (CA), basic compounds whose basicity decreases or disappears upon irradiation with active light or radiation (CB), low molecular weight compounds (CD) having a nitrogen atom and a group that is eliminated by the action of acid, and onium salt compounds (CE) having a nitrogen atom in the cation portion. In resist compositions, known acid diffusion control agents can be used as appropriate. For example, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458A1 can be suitably used as acid diffusion control agents. Furthermore, for example, basic compounds (CA) include those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824, basic compounds (CB) whose basicity is reduced or lost by irradiation with active light or radiation include those described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824, low molecular weight compounds (CD) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824, and onium salt compounds (CE) having a nitrogen atom in the cation include those described in paragraph

[0164] of International Publication No. 2020 / 066824.

[0286] Furthermore, onium salt compounds, which are relatively weak acids relative to the photoacid-generating components, can also be used as acid diffusion control agents. When a photoacid generator (photoacid generators PG1 and PG2 are collectively referred to as photoacid generating components) and an onium salt compound that generates an acid that is relatively weak to the acid produced by the photoacid generating components are used together, when the acid produced by the photoacid generating components collides with the onium salt compound having an unreacted weak acid anion due to irradiation with active light or radiation, salt exchange occurs, releasing the weak acid and producing an onium salt compound having a strong acid anion. In this process, the strong acid is exchanged for a weaker acid with lower catalytic activity, so the acid is seemingly deactivated and acid diffusion can be controlled.

[0287] As onium salt compounds that are relatively weak acids with respect to the photoacid generating component, compounds represented by formulas (d1-1) to (d1-3) are preferred.

[0288] [ka]

[0289] In the formula, R 51 It is an organic group. The number of carbon atoms is preferably 1 to 30. Z 2c is an organic group. The number of carbon atoms in the above organic group is preferably 1 to 30. However, Z 2c The organic group represented by the formula is SO, which is explicitly shown in the formula. 3- When a carbon atom is adjacent to it, this carbon atom (α-carbon atom) does not have a fluorine atom and / or a perfluoroalkyl group as substituents. The above α-carbon atom is preferably a methylene group, and is not a ring member atom of a cyclic structure. Also, Z 2c Medium, SO3 - If the atom at the β position is a carbon atom (β-carbon atom), then the β-carbon atom also does not have a fluorine atom and / or a perfluoroalkyl group as substituents. R 52 Y is an organic group (alkyl group, etc.), 3 is a -SO2-, linear, branched, or cyclic alkylene group or arylene group, Y 4 Rf is a hydrocarbon group containing a fluorine atom (such as a fluoroalkyl group), where -CO- or -SO2- is present.

[0290] M + Each of these is independently an ammonium cation, a sulfonium cation, or an iodonium cation. M in formulas (d1-1) to (d1-3) + As an example, in the above section on <polarity-reducing groups, interacting groups, and polar groups>, the M in the group represented by formula (O1), which is an onium base that is a form of polarity-reducing group, is present. A + Examples include organic cations similar to those represented by [the formula shown]. In one embodiment, it is also preferable that these cations have an acid-degradable group.

[0291] A zwitterion may be used as the acid diffusion control agent. The zwitterion acid diffusion control agent preferably has a carboxylate anion, and more preferably has a sulfonium cation or an iodonium cation.

[0292] If the resist composition contains an acid diffusion control agent, the content of the acid diffusion control agent (total if multiple types exist) is preferably 0.1% by mass or more, and more preferably 1.0% by mass or more, relative to the total solid content of the resist composition. Furthermore, the upper limit is preferably 30.0% by mass or less, more preferably 20.0% by mass or less, and even more preferably 10.0% by mass or less. In the resist composition, one acid diffusion control agent may be used alone, or two or more may be used in combination.

[0293] [Hydrophobic resin] The resist composition may further contain a hydrophobic resin different from the resin described above. Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups in their molecules and do not need to contribute to the uniform mixing of polar and nonpolar substances. The effects of adding hydrophobic resins include controlling the static and dynamic contact angles of the resist film surface with respect to water, as well as suppressing outgassing.

[0294] From the viewpoint of uneven distribution on the film surface, the hydrophobic resin preferably has one or more of the following: fluorine atoms, silicon atoms, and CH3 substructures contained in the side chain portion of the resin, and more preferably two or more. Furthermore, the hydrophobic resin preferably has hydrocarbon groups having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chains. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306.

[0295] If the resist composition contains a hydrophobic resin, the hydrophobic resin content is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% by mass, relative to the total solid content of the resist composition.

[0296] [Surfactants] The resist composition may contain a surfactant. The inclusion of a surfactant improves adhesion and allows for the formation of patterns with fewer development defects. The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of fluorinated and / or silicone-based surfactants include those disclosed in paragraphs

[0218] and

[0219] of International Publication No. 2018 / 193954.

[0297] These surfactants may be used individually or in combination of two or more types.

[0298] If the resist composition contains a surfactant, the surfactant content is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass, relative to the total solid content of the resist composition.

[0299] 〔solvent〕 The resist composition may contain 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, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. This solvent may further contain components other than components (M1) and (M2).

[0300] The inventors have found that using such solvents in combination with the resins described above improves the coatability of the resist composition and enables the formation of patterns with fewer development defects. Although the reason for this is not entirely clear, the inventors believe that these solvents have a good balance of solubility, boiling point, and viscosity with the resins described above, which suppresses unevenness in the film thickness of the resist composition film and the generation of precipitates during spin coating. Details of components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of International Publication No. 2020 / 004306.

[0301] If the solvent further contains components other than components (M1) and (M2), the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total mass of the solvent.

[0302] The solvent content in the resist composition is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably so that it is 1 to 20% by mass. This further improves the coatability of the resist composition.

[0303] [Other additives] The resist composition may further contain a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in the developer (for example, a phenol compound with a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0304] The resist composition may further contain a dissolution-inhibiting compound. Here, a "dissolution-inhibiting compound" is a compound with a molecular weight of 3000 or less that decomposes due to the action of an acid, thereby reducing its solubility in the developer solution.

[0305] The resist composition is suitably used as a photosensitive resist composition for EUV light. EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm), resulting in fewer incident photons when exposed at the same sensitivity. Consequently, the "photon shot noise," where the number of photons varies probabilistically, has a greater impact, leading to deterioration of the LER and bridge defects. One way to reduce photon shot noise is to increase the exposure dose to increase the number of incident photons, but this comes at the cost of higher sensitivity.

[0306] A high A value, calculated using equation (1), indicates that the EUV light and electron beam absorption efficiency of the resist film formed from the resist composition is high, which is effective in reducing photon shot noise. The A value represents the EUV light and electron beam absorption efficiency of the mass percentage of the resist film. Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127) A value of 0.120 or higher is preferable. The upper limit is preferably 0.240 or lower, and more preferably 0.220 or lower, because if the A value is too high, the EUV light and electron beam transmittance of the resist film decreases, the optical image profile in the resist film deteriorates, and as a result it becomes difficult to obtain a good pattern shape.

[0307] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solids to the total atoms of the total solids in the resist composition, [C] represents the molar ratio of carbon atoms derived from the total solids to the total atoms of the total solids in the resist composition, [N] represents the molar ratio of nitrogen atoms derived from the total solids to the total atoms of the total solids in the resist composition, [O] represents the molar ratio of oxygen atoms derived from the total solids to the total atoms of the total solids in the resist composition, [F] represents the molar ratio of fluorine atoms derived from the total solids to the total atoms of the total solids in the resist composition, [S] represents the molar ratio of sulfur atoms derived from the total solids to the total atoms of the total solids in the resist composition, and [I] represents the molar ratio of iodine atoms derived from the total solids to the total atoms of the total solids in the resist composition. For example, if the resist composition contains resin (A), a photoacid generator, an acid diffusion control agent, and a solvent, then the resin (A), the photoacid generator, and the acid diffusion control agent constitute the solid content. In other words, the total atoms of the total solid content refer to the sum of all atoms derived from resin (A), all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content. Based on the above example, [H] represents the molar ratio of the total hydrogen atoms derived from resin (A), all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent to the sum of all atoms derived from resin (A), all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent.

[0308] The A value can be calculated by determining the atomic ratio of the constituent components if the structure and content of the total solid components in the resist composition are known. Even if the constituent components are unknown, the atomic ratio of the constituent components can be calculated by analytical methods such as elemental analysis of the resist film obtained by evaporating the solvent components of the resist composition.

[0309] [Manufacturing methods for electronic devices] This method can also be applied to the manufacturing method of electronic devices, including the pattern formation method described above. The above-mentioned electronic devices are suitably mounted in electrical and electronic equipment (such as home appliances, office automation (OA) equipment, media-related equipment, optical equipment, and communication equipment). [Examples]

[0310] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited to the examples shown below.

[0311] [Preparation of resist composition] The following components were mixed to prepare a mixture. Polymer 1 54 parts by mass Photoacid generator: 31 parts by mass Acid diffusion control agent: 15 parts by mass Propylene glycol monomethyl ether acetate 3430 parts by mass Propylene glycol monomethyl ether 1470 parts by mass

[0312] Polymer 1 is a polymer having the following two repeating units, with a weight-average molecular weight of 8700 and a dispersion degree (Mw / Mn) of 1.23. The molar ratio of the repeating unit represented by U-01 to the repeating unit represented by U-19 was 1:1.

[0313] [ka]

[0314] Photoacid generator (see structural formula below)

[0315] [ka]

[0316] Acid diffusion control agent (see structural formula below)

[0317] [ka]

[0318] Next, the mixture obtained above was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare resist composition R-1.

[0319] [Preparation of drug solution] The chemical solutions for the examples and comparative examples were prepared by mixing the components and their respective contents as shown in the table below. The content of metal X was adjusted by passing the prepared chemical solution through a filter until it reached a predetermined content, or by adding metal X. The water content in each chemical solution was adjusted to 20 to 1000 ppm by mass relative to the total mass of each solution. The content of various components in each chemical solution was calculated from the amount used, or measured using the methods for measuring the content of various components described above. The organic solvent content is calculated by subtracting the total mass of aromatic hydrocarbons, metal X, alcohol compounds, sulfur-containing compounds, and water from the total mass of the chemical solution.

[0320] [Aliphatic hydrocarbons] · Undekan Hexane Hexadecan

[0321] [Ester-based solvents] Butyl acetate • Ethyl acetate · Hexyl acetate

[0322] [Aromatic hydrocarbons] ·C1: 1-ethyl-3,5-dimethyl-benzene(C 10 H 14 ) ·C2: 1,2,3,5-tetramethyl-benzene(C 10 H 14 ) ·C3: (1-methybutyl)-benzene(C 11 H 16 ) ·C4: 1,2,3,4-tetrahydro-naphthalene(C 10 H 12 )

[0323] [Alcohol compounds] ·1-Butanol ·methanol

[0324] [Sulfur-containing compounds] • Benzothiophene • Dimethyl sulfide

[0325] [Examples 1-1 to 1-27 and Comparative Examples 1-1 to 1-5] [Formation of resist film, pattern formation (development)] A 12-inch silicon wafer was coated with the underlayer film formation composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. The resist composition R-1 prepared above was then coated on top of this underlayer and baked (PB) at 90°C for 60 seconds to form a resist film with a thickness of 35 nm. This resulted in the fabrication of a silicon wafer with a resist film. A silicon wafer with the obtained resist film was patterned using an EUV exposure system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A photomask with a line size of 14-25 nm and a line-to-space ratio of 1:1 was used as the rectil. After baking (PEB) at 100°C for 60 seconds, the wafer was developed by paddle for 30 seconds with the developer solutions listed in Tables 1 and 2, and then the wafer was rotated at 4000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 28-50 nm.

[0326] 〔evaluation〕 <Resolution Evaluation> In the above [resist film formation, pattern formation (development)], the exposure amount that reproduces a pattern with a line size of 14-25 nm and a line:space ratio of 1:1 is the optimal exposure amount for each line size (unit: mJ / cm²). 2 ) The critical resolution (the minimum line width at which lines and spaces are separated and resolved) at the optimal exposure level described above was defined as resolution (unit: nm). The evaluation criteria are as follows. In practical terms, an evaluation result of "C" or higher is preferable. A: Less than 18.0 nm B: 18.0nm or more and less than 19.0nm C: 19.0nm or more and less than 20.0nm D: 20.0nm or more and less than 21.0nm E:21.0nm or more

[0327] <Evaluation of defect prevention capabilities> After forming the patterns obtained above, the defect distribution on the silicon wafer was detected using UVision5 (AMAT), and the shape of the defects was observed using SEMVisionG4 (AMAT). The number of defects per silicon wafer was counted and evaluated according to the following evaluation criteria. A lower number of defects indicates a better result. A: Less than 50 B: 50 or more but less than 200 C: 200 or more, less than 300 D: 300 or more, less than 400 E: 400 or more

[0328] [Examples 2-1 to 2-29 and Comparative Examples 2-1 to 2-5] [Formation of resist film, pattern formation (rinsing solution)] A resist film with a thickness of 35 nm was formed using the same procedure as described above for forming the resist film. A silicon wafer having the obtained resist film was patterned using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A photomask with a line size of 14-25 nm and a line-to-space ratio of 1:1 was used as the rectil. After baking (PEB) at 100°C for 60 seconds, the wafer was developed by paddleding with the developer solutions in Tables 3 and 4 for 30 seconds. The wafer was then rinsed by running the rinse solutions in Tables 3 and 4 over it for 10 seconds while rotating it at 1000 rpm, and then rotated at 4000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 28-50 nm.

[0329] The patterns obtained above were evaluated using the same procedure and evaluation criteria as those used for the resolution evaluation and the defect suppression evaluation.

[0330] In the table below, each entry indicates the following: The "Content (a)" column for "Organic Solvents" indicates the mass ratio of the aliphatic hydrocarbon content to the total mass of the organic solvent. The "Content (b)" column for "Organic Solvents" indicates the content of ester-based solvents relative to the total mass of organic solvents. The "total" column for "aromatic hydrocarbons" indicates the total content of aromatic hydrocarbons C1-C4 relative to the total mass of the chemical solution. The columns for "C1" to "C4" under "Aromatic Hydrocarbons" indicate the content (mass ppm) of each aromatic hydrocarbon C1 to C4 relative to the total mass of the chemical solution. The "total" column for "Metal X" shows the total content (mass ppt) of Fe, Ni, and Al relative to the total mass of the chemical solution. The columns for "Fe," "Ni," and "Al" under "Metal X" indicate the respective content (mass ppt) of Fe, Ni, and Al relative to the total mass of the chemical solution. The column "(c) / (e)" shows the mass ratio of the aromatic hydrocarbon content to the metal X content (total content of Fe, Ni, and Al) (aromatic hydrocarbon content / metal X content (total content of Fe, Ni, and Al)). Also, "E+n" is "×10 n This indicates "En" is "×10 -n This indicates that n is a non-negative integer. Specifically, "1.2E+06" is "1.2 × 10 6 This indicates "". Note that "E+n" and "En" above have the same meaning in other columns as well. The "Content" column for "Alcohol Compounds" shows the content of alcohol compounds (mass ppm) relative to the total mass of the drug solution. The "(c) / (f)" column shows the mass ratio of aromatic hydrocarbon content to alcohol compound content (aromatic hydrocarbon content / alcohol compound content). The "Sulfur-containing compound" column shows the amount of sulfur-containing compound (mass ppm) relative to the total mass of the drug solution. The "(c) / (g)" column indicates the mass ratio of aromatic hydrocarbon content to sulfur-containing compound content (aromatic hydrocarbon content / sulfur-containing compound content).

[0331] [Table 1]

[0332] [Table 2]

[0333] [Table 3]

[0334] [Table 4]

[0335] The evaluation results shown in the table above confirm that the chemical solution of the present invention exhibits excellent resolution of the patterns obtained when used as a developer or rinse solution, as well as excellent ability to suppress the occurrence of defects. It was confirmed that resolution is superior when the aliphatic hydrocarbon content is 3 to 30% by mass (preferably 8 to 18% by mass) relative to the total mass of the organic solvent (comparison of Examples 1-1 to 1-10, etc.). Furthermore, from similar comparisons, it was confirmed that resolution is superior when the aliphatic hydrocarbon content is 3 to 30% by mass (preferably 8 to 18% by mass) relative to the total mass of the chemical solution. It was confirmed that resolution is better when the aromatic hydrocarbon includes at least one selected from the group consisting of decane, undecane, dodecane, and methyldecane (comparison of Examples 1-4, 1-11, and 1-12, etc.). It was confirmed that the resolution was superior when the ester-based solvent contained butyl acetate (comparison of Examples 1-4, 1-13, and 1-14, etc.). It was confirmed that the resolution was superior when the alcohol compound contained 1-butanol (comparison of Examples 1-4, 1-15, and 1-16, etc.). It was confirmed that resolution is superior when the alcohol compound content is 0.1 to 5000 ppm by mass relative to the total mass of the drug solution (comparison of Examples 1-4 and 1-23 to 1-24, etc.). It was confirmed that when the content of metal X (total content of Fe, Ni, and Al) is between 0.1 and 50 mass ppt, the ability to suppress defect occurrence is superior (comparison of Examples 1-4, 1-17, and 1-18, etc.). It was confirmed that when the aromatic hydrocarbon content is 5 to 1000 ppm by mass relative to the total mass of the chemical solution, resolution and defect suppression are superior (comparison of Examples 1-4, 1-19, and 1-20, etc.). It was confirmed that resolution and defect suppression are superior when the mass ratio of aromatic hydrocarbons to alcohol compounds (aromatic hydrocarbon content / alcohol compound content) is between 0.001 and 200 (comparison of Examples 1-4, 1-23, and 1-24, etc.). It was confirmed that when the mass ratio of aromatic hydrocarbons to sulfur-containing compounds (aromatic hydrocarbon content / sulfur-containing compound content) is 100 or higher, resolution and defect suppression are superior (comparison of Examples 1-4 and 1-25, etc.). The mass ratio of aromatic hydrocarbon content to metal X content (aromatic hydrocarbon content / metal X content) is 3.0 × 10⁻⁶ 5 ~1.0×10 9 In this case, it was confirmed that resolution or defect suppression was superior (comparison of Examples 1-4, 1-26, and 1-27, etc.).

[0336] It was confirmed that resolution is superior when the aliphatic hydrocarbon content is 5 to 90% by mass relative to the total mass of the drug solution (comparison of Examples 2-1 to 2-10, etc.). Furthermore, similar comparisons confirmed that resolution is even superior when the aliphatic hydrocarbon content is 5 to 90% by mass relative to the total mass of the drug solution. It was confirmed that resolution is better when the aromatic hydrocarbon includes at least one selected from the group consisting of hexane, decane, undecane, dodecane, and methyldecane (comparison of Examples 2-4, 2-11, and 2-12, etc.). It was confirmed that the resolution was superior when the ester-based solvent contained butyl acetate (comparison of Examples 2-4, 2-13, and 2-14, etc.). It was confirmed that the effects of the present invention are superior when the drug solution contains an alcohol compound (comparison of Examples 2-6 and 2-28, etc.). It was confirmed that the resolution was better when the alcohol compound contained 1-butanol (comparison of Examples 2-4, 2-15, and 2-16, etc.). It was confirmed that resolution is superior when the alcohol compound content is 0.1 to 5000 ppm by mass relative to the total mass of the drug solution (comparison of Examples 2-4, 2-23, and 2-24, etc.). It was confirmed that when the content of metal X (total content of Fe, Ni, and Al) is between 0.1 and 50 mass ppt, the ability to suppress defect occurrence is superior (comparison of Examples 2-4, 2-17, and 2-18, etc.). It was confirmed that when the aromatic hydrocarbon content is 5 to 1000 ppm by mass relative to the total mass of the chemical solution, resolution and defect suppression are superior (comparison of Examples 2-4, 2-18, and 2-19, etc.). It was confirmed that resolution and defect suppression are superior when the mass ratio of aromatic hydrocarbons to alcohol compounds (aromatic hydrocarbon content / alcohol compound content) is between 0.001 and 200 (comparison of Examples 2-4, 2-23, and 2-24, etc.). It was confirmed that when the mass ratio of aromatic hydrocarbons to sulfur-containing compounds (aromatic hydrocarbon content / sulfur-containing compound content) is 100 or higher, resolution and defect suppression are superior (comparison of Examples 2-4 and 2-25, etc.). The mass ratio of aromatic hydrocarbon content to metal X content (aromatic hydrocarbon content / metal X content) is 3.0 × 10⁻⁶ 5 ~1.0×10 9 In this case, it was confirmed that resolution or defect suppression was superior (comparison of Examples 2-4, 2-26, and 2-27, etc.).

Claims

1. A developer for a photosensitive or radiation-sensitive resin composition, comprising an aromatic hydrocarbon, an organic solvent other than the aromatic hydrocarbon, and a metal X, The aforementioned aromatic hydrocarbon consists only of hydrogen atoms and carbon atoms. The content of the aromatic hydrocarbon is 1% by mass or less relative to the total mass of the developing solution. The aforementioned organic solvent contains an aliphatic hydrocarbon, The metal X is at least one metal selected from the group consisting of Al, Fe, and Ni. The mass ratio of the aromatic hydrocarbon content to the metal X content is 5.0 × 10 ４ ~2.0 x 10 １０ And, The aforementioned aromatic hydrocarbon is C １０ H １４ , C １１ H １６ and C １０ H １２ It includes at least one selected from the group consisting of, The content of the aromatic hydrocarbon is 5 to 2000 ppm by mass relative to the total mass of the developing solution. Furthermore, it contains sulfur-containing compounds, A developer comprising the aforementioned organic solvent, further containing an ester-based solvent.

2. The content of said C １０ H １４ , the content of said C １１ H １６ , and the content of said C １０ H １２ : The developer according to claim 1, wherein all of the contents are greater than the content of the sulfur-containing compound.

3. The developer according to claim 1, wherein the mass ratio of the content of the aromatic hydrocarbon to the content of the sulfur-containing compound is 1 or more.

4. The developer according to claim 1, comprising three or more of the aforementioned aromatic hydrocarbons.

5. Furthermore, it contains water, The developer according to claim 1, wherein the water content is 20 to 1000 ppm by mass with respect to the total mass of the developer.

6. The developer according to claim 1, wherein the content of at least one of Al, Fe, and Ni is 0.1 to 100 ppt by mass with respect to the total mass of the developer.

7. The developer according to claim 1, wherein the aliphatic hydrocarbon comprises at least one selected from the group consisting of decane, undecane, dodecane, and methyldecane.

8. Furthermore, it contains alcohol compounds, The developer according to claim 1, wherein the mass ratio of the content of the aromatic hydrocarbon to the content of the alcohol compound is 0.001 to 200.

9. The developer according to claim 8, wherein the alcohol compound comprises at least one selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, and 2-methyl-1-butanol.

10. A rinse solution for a photosensitive or radiation-sensitive resin composition, comprising an aromatic hydrocarbon, an organic solvent other than the aromatic hydrocarbon, and metal X, The aforementioned aromatic hydrocarbon consists only of hydrogen atoms and carbon atoms. The content of the aforementioned aromatic hydrocarbon is 1% by mass or less relative to the total mass of the rinse solution. The aforementioned organic solvent contains an aliphatic hydrocarbon, The metal X is at least one metal selected from the group consisting of Al, Fe, and Ni. The mass ratio of the aromatic hydrocarbon content to the metal X content is 5.0 × 10 ４ ~2.0 x 10 １０ And, The aforementioned aromatic hydrocarbon is C １０ H １４ , C １１ H １６ and C １０ H １２ It includes at least one selected from the group consisting of, The content of the aromatic hydrocarbon is 5 to 2000 ppm by mass relative to the total mass of the rinse solution. Furthermore, it contains sulfur-containing compounds, A rinsing solution wherein the aforementioned organic solvent further contains an ester-based solvent.

11. A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, An exposure step of exposing the resist film, A pattern forming method comprising a developing step of developing the exposed resist film using a developer according to any one of claims 1 to 9.

12. A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, An exposure step of exposing the resist film, The exposed resist film is developed using butyl acetate in a developing step, A pattern forming method comprising a washing step of washing with the rinsing solution described in claim 10 after the developing step.

13. A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, An exposure step of exposing the resist film, A developing step in which the exposed resist film is developed using a developer according to any one of claims 1 to 9, A pattern forming method comprising a washing step of washing with a rinsing solution after the developing step, The rinse solution is a rinse solution for a photosensitive or radiation-sensitive resin composition, comprising an aromatic hydrocarbon, an organic solvent other than the aromatic hydrocarbon, and metal X. The aforementioned aromatic hydrocarbon consists only of hydrogen atoms and carbon atoms. The content of the aforementioned aromatic hydrocarbon is 1% by mass or less relative to the total mass of the rinse solution. The aforementioned organic solvent contains an aliphatic hydrocarbon, The metal X is at least one metal selected from the group consisting of Al, Fe, and Ni. The mass ratio of the aromatic hydrocarbon content to the metal X content is 5.0 × 10 ４ ~2.0 x 10 １０ And, The aforementioned aromatic hydrocarbon is C １０ H １４ , C １１ H １６ and C １０ H １２ It includes at least one selected from the group consisting of, The content of the aromatic hydrocarbon is 5 to 2000 ppm by mass relative to the total mass of the rinse solution. Furthermore, it contains sulfur-containing compounds, A pattern-forming method wherein the organic solvent further contains an ester-based solvent.

14. A resist film formation step in which a resist film is formed using a photosensitive or radiation-sensitive resin composition, An exposure step of exposing the resist film, A developing step in which the exposed resist film is developed using a developer according to any one of claims 1 to 9, A pattern forming method comprising a washing step of washing with a rinsing solution after the developing step, The rinse solution comprises an aromatic hydrocarbon, an organic solvent other than the aromatic hydrocarbon, and metal X. The aforementioned aromatic hydrocarbon consists only of hydrogen atoms and carbon atoms. The content of the aforementioned aromatic hydrocarbon is 1% by mass or less relative to the total mass of the rinse solution. The aforementioned organic solvent contains an aliphatic hydrocarbon, The metal X is at least one metal selected from the group consisting of Al, Fe, and Ni. The mass ratio of the aromatic hydrocarbon content to the metal X content is 5.0 × 10 ４ ~2.0 x 10 １０ And, The aforementioned aromatic hydrocarbon is C １０ H １４ , C １１ H １６ and C １０ H １２ It includes at least one selected from the group consisting of, The content of the aromatic hydrocarbon is 5 to 2000 ppm by mass relative to the total mass of the rinse solution. Furthermore, it contains sulfur-containing compounds, The organic solvent further comprises an ester-based solvent, and is a rinse solution for a photosensitive or radiation-sensitive resin composition. A pattern forming method wherein the content of the aliphatic hydrocarbon in the rinsing solution relative to the organic solvent is greater than the content of the aliphatic hydrocarbon in the developing solution relative to the organic solvent.

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