Photosensitive or radiosensitive linear resin compositions, photoresist films, patterning methods, and manufacturing methods of electronic devices.

Abstract

This invention provides a photosensitive radioactive or radioactive linear resin composition exhibiting excellent LWR performance and resolution when forming extremely fine patterns, a photoresist film using the aforementioned photosensitive radioactive or radioactive linear resin composition, a pattern forming method, and a method for manufacturing an electronic device. The photosensitive radioactive or radioactive linear resin composition comprises a compound (N) containing anion and a cation having specific substituents, and a resin (A) whose polarity increases due to decomposition by acid action.

Description

Technical Field

[0001] This invention relates to photosensitive radioactive or radioactive linear resin compositions, photoresist films, patterning methods, and manufacturing methods of electronic devices. More specifically, this invention relates to ultra-microlithography processes applicable to manufacturing processes of large-scale integrated circuits (LSI) and high-capacity microchips, nanoimprint dies fabrication processes, and high-density information recording media; photosensitive radioactive or radioactive linear resin compositions suitable for other photosensitive etching processes; photoresist films using the aforementioned photosensitive radioactive or radioactive linear compositions; patterning methods; and manufacturing methods of electronic devices. Prior Technology

[0002] Previously, in the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs, microfabrication was achieved using photoresist lithography. In recent years, with the increasing integration of integrated circuits, there is a demand for forming ultra-fine patterns in sub-micron or quarter-micron regions. Accompanying this, the exposure wavelength has shifted from gamma rays to i-rays, and further to KrF excimer lasers, showing a trend towards shorter wavelengths. Currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as the light source has been developed. Furthermore, as a technique to further improve resolution, a liquid immersion method is being developed, in which a high-refractive-index liquid (hereinafter referred to as "immersion solution") is filled between the projection lens and the sample.

[0003] Furthermore, in addition to excimer laser light, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) light is also under development. Along with this, chemically amplified photoresist compositions that effectively sense various types of radiation and possess excellent sensitivity and resolution have been developed.

[0004] Onium salts are frequently used in photosensitive or radiosensitive linear resin compositions such as photoresist compositions. For example, Patent Documents 1-9 describe photoresist compositions containing strontium salts having groups containing fluorine atoms. [Previous Technical Documents] [Patent Literature]

[0005] Patent Document 1: Japanese Patent Application Publication No. 2019-182861 Patent Document 2: Japanese Patent Application Publication No. 2019-182860 Patent Document 3: Japanese Patent Application Publication No. 2020-180119 Patent Document 4: Japanese Patent Application Publication No. 2020-180118 Patent Document 5: Japanese Patent Application Publication No. 2020-180122 Patent Document 6: Japanese Patent Application Publication No. 2020-180121 Patent Document 7: Japanese Patent Application Publication No. 2020-91376 Patent Document 8: Japanese Patent Application Publication No. 2020-91374 Patent Document 9: Japanese Patent Application Publication No. 2021-71720 Summary of the Invention

[0006] [The problem that the invention aims to solve] In recent years, the miniaturization of formed patterns has continued to advance, demanding photoresist compositions with excellent line width roughness (LWR) and resolution when forming extremely fine patterns, such as 1:1 lines and spatial patterns with linewidths below 16 nm. LWR performance refers to the ability to reduce the LWR of the pattern.

[0007] The objective of this invention is to provide a photosensitive radioactive or radiosensitive linear resin composition that exhibits excellent LWR performance and resolution when forming extremely fine patterns (e.g., 1:1 lines and spatial patterns with a linewidth of less than 16 nm). Furthermore, the objective of this invention is to provide a photoresist film using the above-mentioned photosensitive or radiosensitive linear resin composition, a pattern forming method, and a method for manufacturing electronic devices. [Methods for solving problems]

[0008] The inventors have discovered that the above-mentioned problems can be solved by the following configuration.

[0009] [1] A photosensitive or radiosensitive linear resin composition comprising a compound (N) having an anion and a cation represented by the following general formula (N1) and a resin (A) whose polarity increases by decomposition under the action of an acid.

[0010] [Chemical Formula 1]

[0011] In general formula (N1), RN1, RN2, and RN3 each independently represent a haloalkyl group or a halogen atom. At least one of RN1, RN2, and RN3 represents a haloalkyl group, and at least one represents a halogen atom. k1 represents an integer from 2 to 5. k2 and k3 represent integers from 1 to 5 independently. There exist multiple RN1, which can be the same or different. When there are multiple RN2, these multiple RN2 can be the same or different. When there are multiple R N3s, the multiple R N3s can be the same or different. in, If k1 represents 2, both RN1 are in the interposition; k2 represents 2, both RN2 are in the interposition; and k3 represents 1, then RN3 is in the adjacent position. If k1 represents 2, both RN1 are in the interposition; k2 represents 2, both RN2 are in the interposition; and k3 represents 2, then the two RN3 are not in the interposition at the same time. If k1 represents 2, both RN1 are in the intermediate position; k2 represents 1, RN2 is in the opposite position; and k3 represents 1, then RN3 is in the adjacent or intermediate position. If k1 represents 3, two RN1s are in the intermediate position, one RN1 is in the opposite position, k2 represents 1, RN2 is in the opposite position, and k3 represents 1, then RN3 is in the adjacent or intermediate position. If k1 represents 2, then both RN1 are adjacent; if k2 represents 2, then both RN2 are adjacent; and if k3 represents 1, then RN3 is adjacent. RN4, RN5, and RN6 each independently represent a substituent. RN4, RN5, and RN6 do not represent halogen atoms or haloalkyl groups. When there are multiple R N4s, these multiple R N4s can be the same or different. When there are multiple R N5s, the multiple R N5s can be the same or different. When there are multiple R N6, the multiple R N6 can be the same or different. k4 represents an integer from 0 to 3. k5 and k6 represent integers from 0 to 4 independently. At least two aromatic rings in the general formula (N1) can be linked by single bonds or linker bonds. [2] The photosensitive or radiosensitive linear resin composition as described in [1] satisfies at least one of the following conditions 1 and 2. Condition 1: k1 represents an integer from 2 to 4. In the aromatic ring bonded by R N1, one metaposition has R N1, and the other metaposition does not have R N1. Condition 2: k2 and k3 independently represent integers from 2 to 4. In the aromatic rings bonded by RN2, one metaposition has RN2 and the other metaposition does not have RN2. In the aromatic rings bonded by RN3, one metaposition has RN3 and the other metaposition does not have RN3. [3] The photosensitive or radiosensitive linear resin composition as described in [1] or [2], wherein the cation represented by the above general formula (N1) is a cation represented by the following general formula (N2).

[0012] [Chemical Formula 2]

[0013] In general formula (N2), RN1, RN2, RN3, RN4, RN5, RN6, k2, k3, k4, k5 and k6 have the same meaning as RN1, RN2, RN3, RN4, RN5, RN6, k2, k3, k4, k5 and k6 in general formula (N1). At least two aromatic rings in the general formula (N2) can be linked by single bonds or linker bonds. [4] The photosensitive or radiosensitive linear resin composition as described in any one of [1] to [3], wherein the cation represented by the above general formula (N1) is a cation represented by the following general formula (N3).

[0014] [Chemical Formula 3]

[0015] In general formula (N3), RN1, RN2, RN3, RN4, RN5, RN6 and k4 have the same meaning as RN1, RN2, RN3, RN4, RN5, RN6 and k4 in general formula (N1). k7 and k8 represent integers from 0 to 3 independently. At least two aromatic rings in the general formula (N3) can be linked by single bonds or linker bonds. [5] The photosensitive or radiosensitive linear resin composition as described in [1] or [2], wherein the cation represented by the above general formula (N1) is a cation represented by the following general formula (N4) or (N5).

[0016] [Chemical Formula 4]

[0017] In general formulas (N4) and (N5), RN1, RN2, RN3, RN4, RN5, RN6 and k4 respectively represent the same meaning as RN1, RN2, RN3, RN4, RN5, RN6 and k4 in general formula (N1). k7 and k8 represent integers from 0 to 3 independently. At least two aromatic rings in the general formula (N4) can be linked by single bonds or linker bonds. At least two aromatic rings in the general formula (N5) can be linked by single bonds or linker bonds. [6] The photosensitive or radiosensitive linear resin composition as described in any one of [1] to [5], wherein all halogen atoms represented by RN1, RN2 and RN3 are fluorine atoms. [7] The photosensitive or radiosensitive linear resin composition as described in any one of [1] to [6], wherein all haloalkyl groups represented by RN1, RN2 and RN3 are fluoroalkyl groups. [8] The photosensitive or radiosensitive linear resin composition as described in any one of [1] to [7], wherein at least one of the haloalkyl groups represented by RN1, RN2 and RN3 has 1 to 4 carbon atoms. [9] The photosensitive or radiosensitive linear resin composition as described in any one of [1] to [8], wherein the anion is an organic anion having at least one of the group consisting of a group represented by the following general formula (N6), *-SO3- and *-CO2-.

[0018] [Chemical Formula 5]

[0019] L N1 and L N2 independently represent -SO 2- or -CO-, respectively. * indicates the location of the bond.

[10] A photoresist film formed using any one of the photosensitive radioactive or radiosensitive linear resin compositions described in [1] to [9].

[11] A pattern forming method, which has the following characteristics: A process for forming a photoresist film on a substrate using any one of [1] to [9] photosensitive radioactive or radiosensitive linear resin compositions; The process of exposing the above photoresist film; and The process of developing the exposed photoresist film using a developer.

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

[11] . [Invention Effects]

[0020] According to the present invention, a photoresist or radiosensitive linear resin composition with excellent LWR performance and resolution when forming extremely fine patterns (e.g., 1:1 lines and spatial patterns with a linewidth of 16 nm or less) can be provided. Furthermore, according to the present invention, a photoresist film using the above-described photoresist or radiosensitive linear resin composition, a pattern forming method, and a method for manufacturing electronic devices can be provided. Simple Explanation of the Diagram

[0021] none Implementation

[0022] The present invention will now be described in detail. The following description of the constituent elements is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. Regarding the use of groups (atomic clusters) in this specification, as long as it does not depart from the spirit of this invention, any expression that does not specify substitution or non-substitution includes both groups without substituents and groups containing substituents. For example, the term "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). Furthermore, in this specification, the term "organic group" refers to a group containing at least one carbon atom. Unless otherwise specified, a monovalent substituent is preferred.

[0023] In this specification, there are no particular limitations on the type, position, or number of substituents when the phrase "may have substituents" is used. The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic groups other than hydrogen atoms, and for example, substituents T can be selected from the following substituents.

[0024] (Substituent T) Examples of substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tributoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; aceoxy groups such as acetoxy, propoxy, and benzooxy; acetyl, benzoyl, isobutyl, propenyl, methacrylyl, and methyloxalyl; and methylthio and tributoxy groups. Alkylthioalkyl and other alkylthioalkyl groups; arylthioalkyl and p-tolylthioalkyl and other arylthioalkyl groups; alkyl (e.g., having 1 to 10 carbon atoms); cycloalkyl (e.g., having 3 to 20 carbon atoms); aryl (e.g., having 6 to 20 carbon atoms); heteroaryl; hydroxyl; carboxyl; methyl; sulfonyl; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonamide; silyl; amino; monoalkylamino; dialkylamino; arylamino; nitro; and combinations thereof.

[0025] In this specification, the terms "photochemical rays" or "radiation" may refer to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this manual, the term "light" refers to photochemical rays or radiation. In this specification, the term "exposure" unless otherwise specified includes exposure using bright-line spectra such as mercury lamps, far-ultraviolet light (represented by excimer lasers), extreme ultraviolet (EUV) light, and X-rays, as well as depiction using particle beams such as electron beams and ion beams. In this manual, the term "~" is used to indicate that the values ​​recorded before and after it are included as lower and upper limits.

[0026] Unless otherwise specified, the bonding orientation of the divalent linker described in this specification is not particularly limited. For example, in compounds represented by the formula "XYZ", when Y is -COO-, Y can be either -CO-O- or -O-CO-. The above compounds can be either "X-CO-OZ" or "XO-CO-Z".

[0027] In this specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic acid means acrylic acid and methacrylic acid. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (hereinafter also referred to as "molecular weight distribution") (Mw / Mn) are defined as polystyrene conversion values ​​obtained by GPC (Gel Permeation Chromatography) apparatus (Tosoh HLC-8120GPC) by GPC determination (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: Tosoh TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL / min, detector: refractive index detector)).

[0028] In this specification, the so-called acid dissociation constant (pKa) refers to the pKa in aqueous solution. Specifically, it is a value obtained by calculation using the following software package 1, based on a database of Hammett substituent constants and known literature values. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0029] pKa can also be obtained using molecular orbital calculations. One specific method is to calculate it using the H+ dissociation free energy in aqueous solution based on thermodynamic cycles. Methods for calculating the H+ dissociation free energy include, for example, DFT (Density Functional Theory), but are not limited to this; various other methods have been reported in the literature. Furthermore, several software programs are available for implementing DFT, such as Gaussian16.

[0030] In this specification, pKa, as mentioned above, refers to the value obtained by using software package 1 to calculate the value based on a database of Hammett substituent constants and known literature values. However, when pKa cannot be calculated using this method, the value obtained by Gaussian 16 based on DFT (density functional theory) is used. In this specification, pKa, as shown above, refers to "pKa in aqueous solution". However, if the pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be used.

[0031] The term "solid component" refers to the component that forms a photosensitive or radiosensitive linear film (typically a photoresist film) and does not contain solvents. Furthermore, as long as it forms a photosensitive or radiosensitive linear film, it is considered a solid component even if it is in liquid form.

[0032] The present invention will now be described in detail.

[0033] [Photosensitive or radiosensitive linear resin composition] The photosensitive or radiosensitive linear resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains a compound (N) having an anion and a cation represented by the following general formula (N1) and a resin (A) whose polarity increases by decomposition under the action of acid.

[0034] [Chemical Formula 6]

[0035] In general formula (N1), RN1, RN2, and RN3 each independently represent a haloalkyl group or a halogen atom. At least one of RN1, RN2, and RN3 represents a haloalkyl group, and at least one represents a halogen atom. k1 represents an integer from 2 to 5. k2 and k3 represent integers from 1 to 5 independently. There exist multiple RN1, which can be the same or different. When there are multiple RN2, these multiple RN2 can be the same or different. When there are multiple R N3s, the multiple R N3s can be the same or different. in, If k1 represents 2, both RN1 are in the interposition; k2 represents 2, both RN2 are in the interposition; and k3 represents 1, then RN3 is in the adjacent position. If k1 represents 2, both RN1 are in the interposition; k2 represents 2, both RN2 are in the interposition; and k3 represents 2, then the two RN3 are not in the interposition at the same time. If k1 represents 2, both RN1 are in the intermediate position; k2 represents 1, RN2 is in the opposite position; and k3 represents 1, then RN3 is in the adjacent or intermediate position. If k1 represents 3, two RN1s are in the intermediate position, one RN1 is in the opposite position, k2 represents 1, RN2 is in the opposite position, and k3 represents 1, then RN3 is in the adjacent or intermediate position. If k1 represents 2, then both RN1 are adjacent; if k2 represents 2, then both RN2 are adjacent; and if k3 represents 1, then RN3 is adjacent. RN4, RN5, and RN6 each independently represent a substituent. RN4, RN5, and RN6 do not represent halogen atoms or haloalkyl groups. When there are multiple R N4s, these multiple R N4s can be the same or different. When there are multiple R N5s, the multiple R N5s can be the same or different. When there are multiple R N6, the multiple R N6 can be the same or different. k4 represents an integer from 0 to 3. k5 and k6 independently represent integers from 0 to 4; At least two aromatic rings in the general formula (N1) can be linked by single bonds or linker bonds.

[0036] The composition of this invention is typically a photoresist composition, which can be a positive photoresist composition or a negative photoresist composition. The photoresist composition can be a photoresist composition for alkaline development or a photoresist composition for organic solvent development. The photoresist composition of this invention can be a chemically amplified photoresist composition or a non-chemically amplified photoresist composition. Preferably, the composition of this invention is a chemically amplified photoresist composition. The film formed using the composition of this invention is a photosensitive radioactive or radiosensitive linear film, typically a photoresist film.

[0037] While the reasons for the excellent LWR performance and resolution of the components of the present invention when forming extremely fine patterns (e.g., 1:1 lines and spatial patterns with a linewidth of less than 16 nm) have not been explained in detail, the inventors speculate as follows. The compound (N) included in the composition of this invention has a cation in each of the three aromatic rings (aryl groups) having at least one of a halogen atom and a haloalkyl group, and the compound as a whole has both a halogen atom and a haloalkyl group. Furthermore, under certain conditions, the cations in compound (N) satisfy specific conditions regarding the substitution positions of the halogen atom and the haloalkyl group. This results in compound (N) having higher cation decomposition efficiency, increased acid production, and improved LWR performance when forming extremely fine patterns. In addition, the cation decomposition products of compound (N) can suppress acid diffusion, making it difficult for acid to diffuse in the exposure zone, thus improving resolution.

[0038] <Compound (N)> Compound (N) is a compound that contains at least one cation (strontium ion) represented by the general formula (N1). Cations represented by the general formula (N1) are also called "specific cations". The compound (N) preferably contains anion in addition to at least one specific cation. In addition to at least one specific cation, a compound (N) may also contain other cations. Depending on the type of anion, the compound (N) can function as both a photoacid generator and an acid diffusion control agent (quencher). Furthermore, compound (N) can also act as a resin (A) whose polarity increases due to decomposition by acid.

[0039] The molecular weight of compound (N) is not limited; it can be a low molecular weight compound or a high molecular weight compound. When compound (N) is a low molecular weight compound, the molecular weight of compound (N) is preferably 200~3500, more preferably 300~3000, and even more preferably 400~2500. When compound (N) is a polymer, the weight-average molecular weight (Mw) of compound (N) is preferably 3,500 to 50,000, more preferably 4,000 to 40,000, and even more preferably 5,000 to 30,000. When compound (N) is a polymer, the dispersion (molecular weight distribution, Mw / Mn) of compound (N) is preferably 1~5, more preferably 1~3, further preferably 1.2~3.0, and especially preferably 1.2~2.0. As an example of a compound (N) being a polymer, examples include resins containing a cation represented by general formula (N1) and an anion. For example, a resin (N) that also functions as a resin (A) whose polarity increases upon decomposition by acid action can be considered. In this case, resin (A) preferably has repeating units containing photoacid-generating groups, and the cation contained in the photoacid-generating groups is a cation represented by general formula (N1). As another example of a compound (N) that also functions as a resin (A) whose polarity increases upon decomposition by acid action, examples include polymers that have anions and cations represented by general formula (N1), and also have repeating units as described later in the description of resin (A) whose polarity increases upon decomposition by acid action. In such examples, photosensitive or radiosensitive linear resin compositions may additionally contain resin (A), but it is also preferable not to contain resin (A). Furthermore, as examples of compounds (N) being macromolecular compounds, examples can also be given of resins containing cations represented by the general formula (N1) and anions.

[0040] (Cations represented by the general formula (N1)) The cation represented by the general formula (N1) will be explained.

[0041] In the general formula (N1), RN1, RN2 and RN3 independently represent haloalkyl or halogen atoms. The halogen atoms represented by RN1, RN2 and RN3 are preferably fluorine, chlorine, bromine or iodine atoms, more preferably fluorine, chlorine or iodine atoms, and most preferably fluorine atoms.

[0042] The alkyl halogroups represented by RN1, RN2, and RN3 can be straight-chain or branched. The number of carbon atoms in the alkyl halogroup is not particularly limited, but is preferably 1 to 12, more preferably 1 to 8, further preferably 1 to 5, particularly preferably 1 to 4, and most preferably 1 to 3. The alkyl halogroup can be a group in which some (at least one) hydrogen atoms of an alkyl group are replaced by halogen atoms, or it can be a group in which all hydrogen atoms of an alkyl group are replaced by halogen atoms. The number of carbon atoms in the alkyl halogens represented by RN1, RN2 and RN3 is preferably such that at least one of the alkyl halogens represented by RN1, RN2 and RN3 has a number of carbon atoms within the above range, and more preferably all the alkyl halogens represented by RN1, RN2 and RN3 have a number of carbon atoms within the above range. The haloalkyl group may have substituents. Examples of substituents include the substituent T mentioned above (wherein, excluding the halogen atom). When the substituent is an organogroup, the organogroup preferably has 1 to 12 carbon atoms, more preferably 1 to 8, further preferably 1 to 5, and most preferably 1 to 4.

[0043] The alkyl halogroups represented by RN1, RN2 and RN3 are preferably alkyl groups having at least one of fluorine, chlorine, bromine and iodine atoms, more preferably alkyl groups having at least one of fluorine and iodine atoms, further preferably fluoroalkyl groups, and most preferably perfluoroalkyl groups.

[0044] In general formula (N1), at least one of RN1, RN2, and RN3 represents a haloalkyl group, and at least one represents a halogen atom. That is, in general formula (N1), at least one of k1 RN1, k2 RN2, and k3 RN3 represents a haloalkyl group, and at least one represents a halogen atom. At least one of RN1, RN2 and RN3 preferably represents a fluorine atom. Preferably, all halogen atoms represented by RN1, RN2 and RN3 are fluorine atoms. At least one of RN1, RN2 and RN3 preferably represents a fluoroalkyl group, and more preferably a perfluoroalkyl group. Preferably, all haloalkyl groups represented by RN1, RN2 and RN3 are fluoroalkyl groups, and more preferably perfluoroalkyl groups. There exist multiple RN1, which can be the same or different. When there are multiple RN2, these multiple RN2 can be the same or different. When there are multiple R N3s, the multiple R N3s can be the same or different.

[0045] k1 represents an integer from 2 to 5. k1 is preferably an integer from 2 to 4, more preferably 2 or 3, and even more preferably 2.

[0046] k2 and k3 each independently represent integers from 1 to 5. k2 and k3 preferably each independently represent integers from 1 to 4, more preferably integers from 1 to 3, and even more preferably 1 or 2.

[0047] The substitution positions of RN1, RN2 and RN3 in the general formula (N1) are not restricted. If RN1, RN2, k1, k2 and k3 meet any of the conditions in (1) to (5) below, then RN3 is subject to the substitution position restrictions described in (1) to (5) below. (1) If k1 represents 2, both R N1 are in the middle position, k2 represents 2, both R N2 are in the middle position, and k3 represents 1, then R N3 is in the adjacent position. (2) If k1 represents 2, both R N1 are in the interposition, k2 represents 2, both R N2 are in the interposition, and k3 represents 2, then the two R N3 are not in the interposition at the same time. (3) If k1 represents 2, both R N1 are in the intermediate position, k2 represents 1, R N2 is in the opposite position, and k3 represents 1, then R N3 is in the adjacent or intermediate position. (4) If k1 represents 3, two R N1s are in the intermediate position, one R N1 is in the opposite position, k2 represents 1, R N2 is in the opposite position, and k3 represents 1, then R N3 is in the adjacent or intermediate position. (5) If k1 represents 2, both RN1 are adjacent, k2 represents 2, both RN2 are adjacent, and k3 represents 1, then RN3 is adjacent. Except for the special cases mentioned above, the substitution sites of RN3 are not restricted.

[0048] In the general formula (N1), the ortho, meta, and para positions represent the positions on the aryl group relative to the sulfur atom. Specifically, in the following general formula (M1), the position substituted by Ro is the ortho position, the position substituted by Rm is the meta position, and the position substituted by Rp is the para position.

[0049] [Chemical Formula 7]

[0050] In the general formula (M1), Ro, Rm, and Rp represent substituents.

[0051] In the general formula (N1), RN4, RN5, and RN6 independently represent substituents. RN4, RN5, and RN6 do not represent halogen atoms or haloalkyl groups. That is, RN4, RN5, and RN6 are different from RN1, RN2, and RN3. RN4, RN5 and RN6 are preferably free of halogen atoms. Substituents represented by RN4, RN5 and RN6, for example, the substituent T mentioned above (excluding the halogen atom), are preferably hydroxyl, cyano, nitro or organogroup. When RN4, RN5, and RN6 represent organic groups, the number of carbon atoms in the organic group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The above-mentioned organic groups are not particularly limited, but are preferably alkyl, cycloalkyl, alkenyl, aryl, heterocyclic, alkoxy, aryloxy, heterocyclic, alkylcarbonyloxy, arylcarbonyloxy, acetyl, alkoxycarbonyl, or aryloxycarbonyl, and more preferably alkyl or alkoxy. Alkyl groups can be linear or branched. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. Alkoxy groups can be linear or branched. Examples of alkoxy groups include methoxy and ethoxy. Aryl groups can be monocyclic or polycyclic. Examples of aryl groups include phenyl, naphthyl, and anthracene, and are preferably phenyl or naphthyl, and more preferably phenyl. The heterocyclic group can be either aromatic or non-aromatic. Preferably, it is a 5-membered or 6-membered ring group. More preferably, it is a fused-ring group composed of 5-membered rings and 5- or 6-membered rings. Also preferably, it is a fused-ring group composed of 6-membered rings and 5- or 6-membered rings. As an aromatic heterocyclic group (heteroaryl), it is preferably an aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The carbon atom that is a ring member in the aromatic heterocyclic group can also be replaced by an oxo group (=O). As a non-aromatic heterocyclic group (aliphatic heterocyclic group), it is preferably a non-aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The carbon atom that is a ring member in the non-aromatic heterocyclic group can be replaced by an oxo group (=O). The aforementioned organogroup may have substituents. Examples of substituents include the aforementioned substituent T (wherein, excluding the halogen atom).

[0052] When there are multiple R N4s, these multiple R N4s can be the same or different. When there are multiple R N5s, the multiple R N5s can be the same or different. When there are multiple R N6, the multiple R N6 can be the same or different.

[0053] k4 represents an integer from 0 to 3. k4 is preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0. k5 and k6 independently represent integers from 0 to 4; k5 and k6 preferably represent integers from 0 to 2, more preferably represent 0 or 1, and even more preferably represent 0. When k4, k5, and k6 represent integers greater than 1, there are no special restrictions on the substitution positions of RN4, RN5, and RN6.

[0054] At least two aromatic rings in general formula (N1) can be linked by single bonds or linking groups. Preferably, the linking group is -O-, -CO-, -SO2-, -S-, -SO-, a hydrocarbon group (e.g., alkyl, cycloalkyl, alkenyl, aryl, etc.), or a divalent linking group selected from two or more of these, more preferably -CO- or -SO2-.

[0055] The compound (N) preferably satisfies at least one of conditions 1 and 2 below. Preferably, by satisfying at least one of conditions 1 and 2 below, the cationic decomposition efficiency of the compound (N) can be further improved. Condition 1: k1 represents an integer from 2 to 4. In the aromatic ring bonded by R N1, one metaposition has R N1, and the other metaposition does not have R N1. Condition 2: k2 and k3 independently represent integers from 2 to 4. In the aromatic rings bonded by RN2, one metaposition has RN2 and the other metaposition does not have RN2. In the aromatic rings bonded by RN3, one metaposition has RN3 and the other metaposition does not have RN3.

[0056] The cation represented by the general formula (N1) is preferably the cation represented by the general formula (N2) below.

[0057] [Chemical Formula 8]

[0058] In general formula (N2), RN1, RN2, RN3, RN4, RN5, RN6, k2, k3, k4, k5 and k6 have the same meaning as RN1, RN2, RN3, RN4, RN5, RN6, k2, k3, k4, k5 and k6 in general formula (N1). At least two aromatic rings in the general formula (N2) can be linked by single bonds or linker bonds.

[0059] The descriptions, specific examples, and preferred ranges of RN1, RN2, RN3, RN4, RN5, RN6, k2, k3, k4, k5, and k6 in general formula (N2) are the same as those for RN1, RN2, RN3, RN4, RN5, RN6, k2, k3, k4, k5, and k6 in general formula (N1).

[0060] At least two aromatic rings in the general formula (N2) can be linked by single bonds or linking groups. Preferably, the linking group is -O-, -CO-, -SO2-, -S-, -SO-, a hydrocarbon group (e.g., alkyl, cycloalkyl, alkenyl, aryl, etc.), or a divalent linking group selected from two or more of these, more preferably -CO- or -SO2-.

[0061] The cation represented by general formula (N1) and the cation represented by general formula (N2) are preferably cations represented by general formula (N3) below.

[0062] [Chemical Formula 9]

[0063] In general formula (N3), RN1, RN2, RN3, RN4, RN5, RN6 and k4 have the same meaning as RN1, RN2, RN3, RN4, RN5, RN6 and k4 in general formula (N1). k7 and k8 represent integers from 0 to 3 independently. At least two aromatic rings in the general formula (N3) can be linked by single bonds or linker bonds.

[0064] The descriptions, specific examples, and preferred ranges of RN1, RN2, RN3, RN4, RN5, RN6, and k4 in general formula (N3) are the same as those for RN1, RN2, RN3, RN4, RN5, RN6, and k4 in general formula (N1).

[0065] In the general formula (N3), k7 and k8 independently represent integers from 0 to 3. k7 and k8 preferably represent integers from 0 to 2, more preferably represent 0 or 1, and even more preferably represent 0.

[0066] At least two aromatic rings in general formula (N3) can be linked by single bonds or linking groups. Preferably, the linking group is -O-, -CO-, -SO2-, -S-, -SO-, a hydrocarbon group (e.g., alkyl, cycloalkyl, alkenyl, aryl, etc.), or a divalent linking group selected from two or more of these, more preferably -CO- or -SO2-.

[0067] The cation represented by the general formula (N1) is also preferably represented by the general formula (N4) or (N5) below.

[0068] [Chemical Formula 10]

[0069] In general formulas (N4) and (N5), RN1, RN2, RN3, RN4, RN5, RN6 and k4 respectively represent the same meaning as RN1, RN2, RN3, RN4, RN5, RN6 and k4 in general formula (N1). k7 and k8 represent integers from 0 to 3 independently. At least two aromatic rings in the general formula (N4) can be linked by single bonds or linker bonds. At least two aromatic rings in the general formula (N5) can be linked by single bonds or linker bonds.

[0070] The descriptions, specific examples, and preferred ranges of RN1, RN2, RN3, RN4, RN5, RN6, and k4 in general formulas (N4) and (N5) are the same as those for RN1, RN2, RN3, RN4, RN5, RN6, and k4 in general formula (N1).

[0071] In general formulas (N4) and (N5), k7 and k8 independently represent integers from 0 to 3. k7 and k8 preferably represent integers from 0 to 2, more preferably represent 0 or 1, and even more preferably represent 0.

[0072] At least two aromatic rings in general formulas (N4) and (N5) can be linked by single bonds or linking groups. Preferably, the linking group is -O-, -CO-, -SO2-, -S-, -SO-, a hydrocarbon group (e.g., alkyl, cycloalkyl, alkenyl, aryl, etc.), or a divalent linking group selected from two or more of these, more preferably -CO- or -SO2-.

[0073] Certain cations may have acid-degradable groups. Regarding acid-degradable groups, the same applies as described in the following description of resin (A). A preferred embodiment is one in which certain cations do not possess acid-degradable groups.

[0074] Specific cations, for example, can be synthesized by methods according to the following literature. ·J. Org. Chem., Vol.53, No.23, 1988, 5571-5573

[0075] Specific examples of particular cations are listed below, but the present invention is not limited thereto.

[0076] [Chemical Formula 11]

[0077] [Chemical Formula 12]

[0078] [Chemical Formula 13]

[0079] The compound (N) is preferably one of the group consisting of a group selected from the general formula (N6) below, *-SO3- and *-CO2-. The compound (N) contains a specific cation and an organic anion, preferably having at least one of the groups selected from the group represented by the following general formula (N6), *-SO3-, and *-CO2-. * indicates the bonding position.

[0080] [Chemical Formula 14]

[0081] In general formula (N6), L N1 and L N2 independently represent -SO 2- or -CO-, respectively. * indicates the location of the bond.

[0082] (Organic anions) A preferred form of compound (N) is a compound represented by "M + X -". M+ represents the specific cation mentioned above. X - represents an organic anion. There are no particular limitations on what constitutes an organic anion; examples of organic anions with a valence of 1 or 2 or higher can be given. As an organic anion, it is preferably an anion with very low ability to induce nucleophilic reactions, and more preferably a non-nucleophilic anion.

[0083] Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, and camphor sulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions, etc.), sulfadiene anions, bis(alkylsulfadiene) sulfadiene anions, and tris(alkylsulfadiene) methylated anions.

[0084] The aliphatic portion of the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion can be a straight-chain or branched alkyl group, or a cycloalkyl group, preferably a straight-chain or branched alkyl group with 1 to 30 carbon atoms, or a cycloalkyl group with 3 to 30 carbon atoms. The aforementioned alkyl group, for example, can be a fluoroalkyl group (which may have substituents other than fluorine atoms. It can also be a perfluoroalkyl group).

[0085] The aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group with 6 to 14 carbon atoms, for example, phenyl, tolyl and naphthyl.

[0086] The alkyl, cycloalkyl, and aryl groups mentioned above may have substituents. There are no particular limitations on the substituents; for example, halogen atoms such as nitro, fluorine, and chlorine, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably 1-15 carbon atoms), alkyl (preferably 1-10 carbon atoms), cycloalkyl (preferably 3-15 carbon atoms), aryl (preferably 6-14 carbon atoms), alkoxycarbonyl (preferably 2-7 carbon atoms), acetyl (preferably 2-12 carbon atoms), alkoxycarbonyloxy (preferably 2-7 carbon atoms), alkylthio (preferably 1-15 carbon atoms), alkylsulfonyl (preferably 1-15 carbon atoms), alkyliminosulfonyl (preferably 1-15 carbon atoms), and aryloxysulfonyl (preferably 6-20 carbon atoms) are also possible.

[0087] The aralkyl group in the aralkyl carboxylic acid anion is preferably an aralkyl group with 7 to 14 carbon atoms. Examples of aryl alkyl groups having 7 to 14 carbon atoms include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl.

[0088] Examples of sulfadiazine anions include, for instance, saccharin anion.

[0089] The alkyl group in the bis(alkylsulfonyl)imine anion and the trialkyl(alkylsulfonyl)methyl anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for such alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, preferably fluorine atoms or alkyl groups substituted with fluorine atoms. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imidin anion can also bond with each other to form a ring structure. This can increase the acid strength.

[0090] Other non-nucleophilic anions include, for example, phosphorus fluoride (e.g., PF6-), boron fluoride (e.g., BF4-), and antimony fluoride (e.g., SbF6-).

[0091] As a non-nucleophilic anion, it is preferably an aliphatic sulfonic acid anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imidion anion in which the alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methylated anion in which the alkyl group is substituted with a fluorine atom. More preferably, it is a perfluoroaliphatic sulfonic acid anion (preferably having 4 to 8 carbon atoms), or a benzenesulfonic acid anion having a fluorine atom, and even more preferably, a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, a pentafluorobenzenesulfonic acid anion, or a 3,5-bis(trifluoromethyl)benzenesulfonic acid anion.

[0092] As a non-nucleophilic anion, it is also preferred to be an anion represented by the following formula (AN1).

[0093] [Chemical Formula 15]

[0094] In formula (AN1), R1 and R2 independently represent hydrogen atoms or substituents, respectively. There are no particular restrictions on the substituents, but they are preferably non-electron-withdrawing groups. Examples of non-electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbonyl groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. The non-electron-withdrawing groups are preferably -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR', each independently and preferably. R' is a monovalent hydrocarbon group.

[0095] Examples of monovalent hydrocarbon groups represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl, propynyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornyl; aryl groups such as phenyl, tolyl, xylyl, trimethylmethyl, naphthyl, methylnaphthyl, anthracene, and methylanthrayl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthracenemethyl. R1 and R2 are each, independently, preferably, a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0096] L represents a divalent linker. When there are multiple Ls, each L can be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining a plurality of these. Among these, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2-, -O-CO-O-alkylene-, -COO-alkylene-, or -CONH-alkylene- are preferred, and more preferably -O-CO-O-, -O-CO-O-alkylene-, -COO-, -CONH-, -SO 2-, or -COO-alkylene-.

[0097] L, for example, is preferably a group represented by the following formula (AN1-1). * a-(CR 2a 2) XQ-(CR 2b 2) Y-* b(AN1-1)

[0098] In equation (AN1-1), *a represents the bond position with R3 in equation (AN1). * b indicates the bond position with -C(R 1)(R 2)- in equation (AN1). X and Y represent integers from 0 to 10, preferably integers from 0 to 3. R 2a and R 2b represent hydrogen atoms or substituents independently, respectively. When there are multiple R2a and R2b respectively, the multiple R2a and R2b can be the same or different. When Y is 1 or more, the R2b atom in CR2b2 that is directly bonded to -C(R1)(R2)- in formula (AN1) is a non-fluorine atom. Q represents *AO-CO-O-*B, *A-CO-*B, *A-CO-O-*B, *AO-CO-*B, *AO-*B, *AS-*B, or *A-SO 2-*B. Where X+Y in formula (AN1-1) is 1 or more, and R2a and R2b in formula (AN1-1) are both hydrogen atoms, Q represents *AO-CO-O-*B, *A-CO-*B, *AO-CO-*B, *AO-*B, *AS-*B, or *A-SO2-*B. * A represents the bond position on the R 3 side in equation (AN1), * B represents the bond position on the -SO 3 - side in equation (AN1).

[0099] In formula (AN1), R3 represents an organic group. There are no particular restrictions on the presence of one or more carbon atoms in the aforementioned organic groups. They can be straight-chain groups (e.g., straight-chain alkyl groups), branched-chain groups (e.g., branched-chain alkyl groups such as tert-butyl), or cyclic groups. The aforementioned organic groups may or may not have substituents. The aforementioned organic groups may or may not have heteroatoms (oxygen atoms, sulfur atoms, and / or nitrogen atoms, etc.).

[0100] R3 is preferably an organic group with a cyclic structure. The cyclic structure can be monocyclic or polycyclic, and can also have substituents. The ring in the organic group containing the cyclic structure is preferably directly bonded to L in formula (AN1). Organic groups having the above-mentioned cyclic structure may or may not have heteroatoms (oxygen, sulfur, and / or nitrogen atoms, etc.). Heteroatoms may replace one or more carbon atoms forming the cyclic structure. The organic group having the above-mentioned cyclic structure is preferably a hydrocarbon group, a lactone cyclic group, or a sulfonyl lactone cyclic group. Among them, the organic group having the above-mentioned cyclic structure is preferably a hydrocarbon group with a cyclic structure. The hydrocarbon group in the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The aforementioned cycloalkyl group can be monocyclic (such as cyclohexyl) or polycyclic (such as adamantyl), with a preferred number of carbon atoms being 5 to 12. As the aforementioned lactone group and sulfonolactone group, for example, in any of the structures represented by formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) described below, it is preferred to be a group formed by removing a hydrogen atom from the ring member atom constituting the lactone structure or sulfonolactone structure.

[0101] As a non-nucleophilic anion, it can be a benzenesulfonic acid anion, preferably a benzenesulfonic acid anion substituted with branched alkyl or cycloalkyl groups.

[0102] As a non-nucleophilic anion, it is also preferred to be an anion represented by the following formula (AN2).

[0103] [Chemical Formula 16]

[0104] In equation (AN2), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0105] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organogroup without a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. As for the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and even more preferably both Xf are fluorine atoms.

[0106] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are multiple R4s and R5s, R4s and R5s may be the same or different. The alkyl group represented by R4 and R5 is preferably composed of 1 to 4 carbon atoms. The alkyl group may have substituents. Hydrogen atoms are preferred as R4 and R5.

[0107] L represents a binary linking basis. The definition of L is synonymous with L in equation (AN1).

[0108] W represents an organic group containing a cyclic structure. Preferably, it is a cyclic organic group. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. Alicyclic groups can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Preferably, these are alicyclic groups with a large volumetric structure, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl.

[0109] The aryl group can be monocyclic or polycyclic. Examples of the aforementioned aryl groups include phenyl, naphthyl, phenanthryl, and anthracene. The heterocyclic group can be monocyclic or polycyclic. When it is a polycyclic heterocyclic group, it can further inhibit acid diffusion. The heterocyclic group can be aromatic or non-aromatic. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocycles include tetrahydropyran rings, lactone rings, sulfonyl lactone rings, and decahydroisoquinoline rings. The preferred heterocycles in the heterocyclic group are furan rings, thiophene rings, pyridine rings, or decahydroisoquinoline rings.

[0110] The aforementioned cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be either linear or branched, preferably with 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably with 3 to 20 carbon atoms), aryl groups (preferably with 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, carbamate groups, urea groups, thioether groups, sulfonamide groups, and sulfonate groups. Furthermore, the carbon atom constituting the cyclic organic group (the carbon atom that contributes to ring formation) may also be a carbonyl carbon.

[0111] The preferred anions represented by formula (AN2) are SO₃-CF₂-CH₂-OCO₃-(L) q'-W, SO₃-CF₂-CHF-CH₂-OCO₃-(L) q'-W, SO₃-CF₂-COO₃-(L) q'-W, SO₃-CF₂-CF₂-CH₂-CH₂-(L) qW, or SO₃-CF₂-CH(CF₃)-OCO₃-(L) q'-W. Here, L, q, and W are the same as in formula (AN2). q' represents an integer from 0 to 10.

[0112] As a non-nucleophilic anion, it is also preferred to be an aromatic sulfonic acid anion represented by the following formula (AN3).

[0113] [Chemical Formula 17]

[0114] In formula (AN3), Ar represents an aryl group (phenyl, etc.), and may further have substituents other than a sulfonic acid anion and a -(DB) group. Examples of substituents that may be further included include, for example, fluorine atoms and hydroxyl groups. n represents an integer greater than or equal to 0. Preferably, n is 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0115] D represents a single bond or a divalent linker. Examples of divalent linkers include ether groups, thioether groups, carbonyl groups, urethane groups, urethane groups, sulfonate groups, ester groups, and groups consisting of two or more of these.

[0116] B represents a hydrocarbon group. As B, it is preferably an aliphatic hydrocarbon group, more preferably isopropyl, cyclohexyl, or an aryl group (such as tricyclohexylphenyl) that may further have substituents.

[0117] As a non-nucleophilic anion, disulfonamide anion is also preferred. For example, the disulfonamide anion is an anion represented by N-(SO₂-Rq)₂. Here, R q represents an alkyl group that may have substituents, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. Two R q groups may bond together to form a ring. The group formed by the bonding of two R q groups is preferably an enylalkyl group that may have substituents, more preferably a fluoroenylalkyl group, and even more preferably a perfluoroenylalkyl group. The enylalkyl group preferably has 2 to 4 carbon atoms.

[0118] Furthermore, as non-nucleophilic anions, anions represented by the following formulas (d1-1) to (d1-4) can also be cited.

[0119] [Chemical Formula 18]

[0120] [Chemical Formula 19]

[0121] In formula (d1-1), R 51 represents a hydrocarbon group (e.g., aryl, such as phenyl) that may have substituents (e.g., hydroxyl).

[0122] In formula (d1-2), Z 2c represents a hydrocarbon group with 1 to 30 carbon atoms that can have substituents (where the carbon atom adjacent to S is not replaced by a fluorine atom). The hydrocarbon group in Z 2c can be linear, branched, or cyclic. Furthermore, the carbon atom in the hydrocarbon group (preferably a carbon atom that is a ring member when the hydrocarbon group has a cyclic structure) can be a carbonyl carbon (-CO-). Examples of hydrocarbon groups include norbornyl groups, which can have substituents. The carbon atom forming the norbornyl group can be a carbonyl carbon. In formula (d1-2), "Z 2c-SO 3 -" is preferably different from the anion represented by formulas (AN1) to (AN3) above. For example, Z 2c is preferably other than an aryl group. For example, in Z 2c, the atoms at the α and β positions relative to -SO 3 - are preferably atoms other than carbon atoms having fluorine atoms as substituents. For example, in Z 2c, the atoms at the α position and / or β position relative to -SO 3 - are preferably ring-member atoms in a cyclic group.

[0123] In formula (d1-3), R52 represents an organic group (preferably a hydrocarbon group with fluorine atoms), Y3 is a linear, branched, or cyclic alkyl, aryl, or carbonyl group, and Rf represents a hydrocarbon group.

[0124] In formula (d1-4), R53 and R54 independently represent organic groups (preferably hydrocarbon groups with fluorine atoms). R53 and R54 can bond together to form a ring.

[0125] Organic anions can be used alone or in combination with two or more.

[0126] The compound (N) is preferably selected from at least one of the groups consisting of compounds (NI) and (NII).

[0127] (Compound (NI)) The compound (NI) is a compound having one or more structural sites X and one or more structural sites Y, and is a compound that, when irradiated by photochemical rays or radiation, produces an acid comprising a first acidic site derived from structural site X and a second acidic site derived from structural site Y. Structural site X: Composed of anionic site A1- and cationic site M1+, and formed by irradiation with photochemical rays or radiation, forming the first acidic site represented by HA1. Structural site Y: Composed of anionic site A2- and cationic site M2+, and formed by irradiation with photochemical rays or radiation, forming a second acidic site represented by HA2. The above compound (NI) satisfies the following condition I.

[0128] Condition I: In the above compound (N1), the compound PNI obtained by replacing the above-mentioned cation M1+ in the above-mentioned structural site X and the above-mentioned cation M2+ in the above-mentioned structural site Y with H+ has an acid dissociation constant a1 derived from the acidic site represented by HA1 obtained by replacing the above-mentioned cation M1+ in the above-mentioned structural site X with H+ and an acid dissociation constant a2 derived from the acidic site represented by HA2 obtained by replacing the above-mentioned cation M2+ in the above-mentioned structural site Y with H+, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0129] The following will provide a more detailed explanation of condition I. When a compound (NI), for example, is used to produce an acid having a first acidic site derived from the above-described structural site X and a second acidic site derived from the above-described structural site Y, the compound PNI is equivalent to "a compound having HA 1 and HA 2". The acid dissociation constants a1 and a2 of compound PNI, more specifically, refer to the pKa of compound PNI when it becomes "a compound having A1- and HA2", given that the acid dissociation constants of compound PNI have been determined, and the pKa of "a compound having A1- and HA2" when it becomes "a compound having A1- and A2-".

[0130] When a compound (NI), for example, is a compound that produces an acid having two first acidic sites derived from the above-described structural site X and one second acidic site derived from the above-described structural site Y, the compound PNI is equivalent to "a compound having two HA 1 and one HA 2". Having determined the acid dissociation constant of compound PNI, the acid dissociation constant when compound PNI is a "compound having one A1-, one HA1, and one HA2" and the acid dissociation constant when "a compound having one A1-, one HA1, and one HA2" becomes "a compound having two A1- and one HA2" are equivalent to the aforementioned acid dissociation constant a1. When "a compound having two A1- and one HA2" becomes "a compound having two A1- and A2-", the acid dissociation constant is equivalent to acid dissociation constant a2. That is, in the case of compound PNI, when there are multiple acid dissociation constants for the acidic site represented by HA1 obtained by replacing the aforementioned cation site M1+ from the aforementioned structural site X with H+, the value of acid dissociation constant a2 is greater than the maximum value among the multiple acid dissociation constants a1. Furthermore, when the acid dissociation constant of compound PNI is defined as "a compound having one A1-, one HA1, and one HA2", and the acid dissociation constant of "a compound having one A1-, one HA1, and one HA2" is defined as "ab", the relationship between aa and ab satisfies aa <ab。

[0131] The acid dissociation constants a1 and a2 can be determined using the methods described above for determining the acid dissociation constants. The compound PNI mentioned above is equivalent to the acid produced when compound (NI) is irradiated with photochemical rays or radiation. When a compound (NI) has two or more structural sites X, the structural sites X may be the same or different. Furthermore, two or more of the above-mentioned A1- and two or more of the above-mentioned M1+ may be the same or different. In compound (NI), the above-mentioned A1- and A2-, as well as the above-mentioned M1+ and M2+, may be the same or different, but the above-mentioned A1- and A2- are preferably different.

[0132] In the aforementioned compound PNI, the absolute value of the difference between the acid dissociation constant a1 (which is 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. Furthermore, there is no particular upper limit to the absolute value of the difference between the acid dissociation constant a1 (which is the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2; for example, it may be 16 or less.

[0133] In the above-mentioned compound PNI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. Furthermore, as a lower limit value of the acid dissociation constant a2, it is preferably -4.0 or more.

[0134] In the above-mentioned compound PNI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. Furthermore, as a lower limit value of the acid dissociation constant a1, it is preferably -20.0 or more.

[0135] Anionic sites A1- and A2- are structural sites containing negatively charged atoms or groups of atoms. For example, structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below can be cited. The anionic site A1- is preferably an acidic site that can form an acid dissociation constant, and more preferably any one of formulas (AA-1) to (AA-3), and even more preferably any one of formulas (AA-1) and (AA-3). Furthermore, the anionic site A2- is preferably an acidic site that can form an acid dissociation constant larger than that of the anionic site A1-, more preferably any one of formulas (BB-1) to (BB-6), and even more preferably any one of formulas (BB-1) and (BB-4). Furthermore, in the following equations (AA-1) to (AA-3) and (BB-1) to (BB-6), * indicates the bond position. In formula (AA-2), RA represents a monovalent organic group. There are no particular limitations on the monovalent organic group represented by RA; for example, cyano, trifluoromethyl, and methanesulfonyl can be cited.

[0136] [Chemical Formula 20]

[0137] [Chemical Formula 21]

[0138] The anionic sites A1- and A2- are preferably composed of at least one of the groups selected from the group represented by the above general formula (N7), -SO3- and -CO2-.

[0139] Cation sites M1+ and M2+ are structural sites containing positively charged atoms or groups of atoms, for example, monovalent organic cations. At least one of M1+ and M2+ is the specific cation mentioned above.

[0140] There are no particular restrictions on the specific structure of the compound (NI). For example, compounds represented by formulas (Ia-1) to (Ia-5) described later can be cited.

[0141] -Compounds represented by formula (Ia-1)- The following section will first describe the compound represented by formula (Ia-1).

[0142] M 11 +A 11 --L 1-A 12 -M 12 +(Ia-1)

[0143] The compound represented by formula (Ia-1) produces an acid represented by HA 11-L 1-A 12H when exposed to photochemical rays or radiation.

[0144] In formula (Ia-1), M11+ and M12+ represent organic cations independently. A11- and A12- represent monovalent anionic functional groups, respectively. L1 represents a bivalent linker. M11+ and M12+ can be the same or different. A11- and A12- can be the same or different, but it is better for them to be different from each other. In formula (Ia-1) above, in compound PNIa (HA 11-L 1-A 12H) formed by replacing the cations represented by M 11+ and M 12+ with H+, the acid dissociation constant a2 derived from the acidic site represented by A 12H is greater than the acid dissociation constant a1 derived from the acidic site represented by HA 11. Furthermore, preferred values ​​for acid dissociation constants a1 and a2 are as described above. Compound PNIa is the same acid produced from the compound represented by formula (Ia-1) by irradiation with photochemical rays or radiation. Furthermore, at least one of M11+, M12+, A11-, A12- and L1 may have an acid-decomposable group as a substituent.

[0145] In formula (Ia-1), at least one of M11+ and M12+ is the specific cation mentioned above.

[0146] The term "monovalent anionic functional group represented by A11-" refers to a monovalent group containing the aforementioned anionic site A1-. Similarly, the term "monovalent anionic functional group represented by A12-" refers to a monovalent group containing the aforementioned anionic site A2-. The monovalent anionic functional group represented by A11- and A12- is preferably a monovalent anionic functional group containing the anionic sites of any one of the above formulas (AA-1) to (AA-3) and (BB-1) to (BB-6), and more preferably a monovalent anionic functional group selected from the group consisting of formulas (AX-1) to (AX-3) and (BX-1) to (BX-7). The monovalent anionic functional group represented by A11- is preferably a monovalent anionic functional group represented by any one of formulas (AX-1) to (AX-3). As a monovalent anionic functional group represented by A 12 -, preferably a monovalent anionic functional group represented by any one of formulas (BX-1) to (BX-7), more preferably a monovalent anionic functional group represented by any one of (BX-1) to (BX-6).

[0147] [Chemical Formula 22]

[0148] In equations (AX-1) to (AX-3), RA1 and RA2 independently represent monovalent organic groups. * indicates the bond position. There are no particular limitations on the monovalent organic groups represented by RA1; for example, cyano, trifluoromethyl, and methanesulfonyl can be cited.

[0149] As a monovalent organic group represented by RA2, it is preferably a straight-chain, branched, or cyclic alkyl or aryl group. The number of carbon atoms in the aforementioned 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. Preferred substituents are fluorine atoms or cyano groups, and more preferably fluorine atoms. When the alkyl group has a fluorine atom as a substituent, it may also be a perfluoroalkyl group.

[0150] The aryl group is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group described above may have substituents. Preferred substituents are fluorine atoms, iodine atoms, perfluoroalkyl groups (e.g., preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or cyano groups, more preferably fluorine atoms, iodine atoms, or perfluoroalkyl groups.

[0151] In equations (BX-1) to (BX-4) and (BX-6), RB represents a monovalent organic group. * indicates a bond position. As a monovalent organic group represented by RB, it is preferably a straight-chain, branched, or cyclic alkyl group, or an aryl group. The number of carbon atoms in the aforementioned 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. There are no particular restrictions on the substituents, but fluorine atoms or cyano groups are preferred, and fluorine atoms are even more preferred. When the alkyl group has a fluorine atom as a substituent, it may also be a perfluoroalkyl group. Furthermore, when the carbon atom at the bonding position in the alkyl group has a substituent, it is preferably a substituent other than a fluorine atom or a cyano group. Here, the carbon atom at the bonding position in the alkyl group, for example, in the cases of formulas (BX-1) and (BX-4), corresponds to a carbon atom directly bonded to the -CO- group of the alkyl group as stated in the formula; in the cases of formulas (BX-2) and (BX-3), corresponds to a carbon atom directly bonded to the -SO2- group of the alkyl group as stated in the formula; and in the case of formula (BX-6), corresponds to a carbon atom directly bonded to the N- group of the alkyl group as stated in the formula. The carbon atoms of the aforementioned alkyl groups can be replaced by carbonyl carbons.

[0152] The aryl group is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group described above may have substituents. Preferred substituents are fluorine atoms, iodine atoms, perfluoroalkyl groups (e.g., preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), cyano groups, alkyl groups (e.g., preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), alkoxy groups (e.g., preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), or alkoxycarbonyl groups (e.g., preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), and more preferably fluorine atoms, iodine atoms, perfluoroalkyl groups, alkyl groups, alkoxy groups, or alkoxycarbonyl groups.

[0153] In equation (Ia-1), there are no particular restrictions on the divalent linking base represented by L 1, and examples include -CO-, -NR-, -O-, -S-, -SO-, and -SO-. 2-, alkyl groups (preferably with 1 to 6 carbon atoms, and can be straight-chain or branched), cycloalkyl groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom within the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom within the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic hydrocarbon cyclocyclic groups (preferably 6 to 10-membered rings, and even more preferably 6-membered rings), and divalent linking groups formed by combining a plurality of these. Examples of R above include hydrogen atoms or monovalent organic groups. There are no particular limitations on the monovalent organic group; for example, it is preferably an alkyl group (preferably having 1 to 6 carbon atoms). The aforementioned alkyl groups, cycloalkyl groups, alkenyl groups, divalent aliphatic heterocyclic groups, divalent aromatic heterocyclic groups, and divalent aromatic hydrocarbon cyclocyclic groups may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0154] Among them, the binary linking basis represented by L1 is preferably the binary linking basis represented by equation (L1).

[0155] [Chemical Formula 23]

[0156] In equation (L1), L111 represents a single bond or a divalent linker. There are no particular limitations on the divalent linker represented by L 111. Examples include -CO-, -NH-, -O-, -SO-, -SO 2-, or alkyl groups (preferably with 1 to 6 carbon atoms, and can be either straight-chain or branched), cycloalkyl groups (preferably with 3 to 15 carbon atoms), aryl groups (preferably with 6 to 10 carbon atoms), and divalent linkers formed by combining multiple of these. There are no particular limitations on the substituents; for example, halogen atoms can be mentioned. p represents an integer from 0 to 3, preferably an integer from 1 to 3. v represents an integer of 0 or 1. Xf 1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. As for the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf2 independently represents a hydrogen atom, an alkyl group that may have a fluorine atom as a substituent, or a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. As Xf2, it is preferably an alkyl group representing a fluorine atom or substituted with at least one fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group. Xf1 and Xf2 are preferably fluorine atoms or perfluoroalkyl groups having 1 to 4 carbon atoms, more preferably fluorine atoms or CF3. In particular, it is even more preferred that both Xf1 and Xf2 are fluorine atoms. * indicates the location of the bond. When L1 in equation (Ia-1) represents a divalent linker represented by equation (L1), the bond (*) on the L111 side of equation (L1) is preferably bonded to A12 in equation (Ia-1).

[0157] -Compounds represented by formulas (Ia-2)~(Ia-4)- Next, the compounds represented by formulas (Ia-2) to (Ia-4) will be described.

[0158] [Chemical Formula 24]

[0159] In formula (Ia-2), A21a- and A21b- each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional group represented by A21a- and A21b- refers to a monovalent group containing the aforementioned anionic site A1-. There is no particular limitation on the monovalent anionic functional group represented by A21a- and A21b-; for example, monovalent anionic functional groups selected from the group consisting of formulas (AX-1) to (AX-3) can be cited. A22- represents a divalent anionic functional group. Here, the term "divalent anionic functional group represented by A22-" refers to a divalent linker containing the aforementioned anionic site A2-. Examples of divalent anionic functional groups represented by A22- include those represented by formulas (BX-8) to (BX-11) shown below.

[0160] [Chemical Formula 25]

[0161] M21a+, M21b+, and M22+ each independently represent an organic cation. At least one of M21a+, M21b+, and M22+ is the specific cation mentioned above. L21 and L22 represent divalent organic groups independently.

[0162] In formula (Ia-2) above, in compound PNIa-2 formed by replacing the organic cations represented by M21a+, M21b+, and M22+ with H+, the acid dissociation constant a2 derived from the acidic site represented by A22H is greater than the acid dissociation constant a1-1 derived from the acidic site represented by A21aH and the acid dissociation constant a1-2 derived from the acidic site represented by A21bH. Furthermore, the acid dissociation constants a1-1 and a1-2 are equivalent to the aforementioned acid dissociation constant a1. Furthermore, A21a- and A21b- can be the same or different. M21a+, M21b+, and M22+ can be the same or different. At least one of M21a+, M21b+, M22+, A21a-, A21b-, L21 and L22 may have an acid-degradable group as a substituent.

[0163] In equation (Ia-3), A31a- and A32- independently represent monovalent anionic functional groups. Furthermore, the definition of a monovalent anionic functional group represented by A31a- is synonymous with A21a- and A21b- in equation (Ia-2) above, and the preferred form is also the same. The monovalent anionic functional group represented by A 32 - refers to a monovalent group containing the aforementioned anionic site A 2 -. There are no particular limitations on the monovalent anionic functional group represented by A 32 -, for example, monovalent anionic functional groups selected from the group consisting of the above formulas (BX-1) to (BX-7) can be cited. A 31b - represents a divalent anionic functional group. Here, the term "divalent anionic functional group" as represented by A 31b - refers to a divalent linker containing the aforementioned anionic site A 1 -. For example, a divalent anionic functional group represented by the formula (AX-4) shown below can be cited as an example of a divalent anionic functional group represented by A 31b -.

[0164] [Chemical Formula 26]

[0165] M31a+, M31b+, and M32+ each independently represent a monovalent organic cation. At least one of M31a+, M31b+, and M32+ is the specific cation mentioned above. L31 and L32 represent divalent organic groups independently.

[0166] In the above formula (Ia-3), in the compound PNIa-3 formed by replacing the organic cations represented by M31a+, M31b+, and M32+ with H+, the acid dissociation constant a2 derived from the acidic site represented by A32H is greater than the acid dissociation constant a1-3 derived from the acidic site represented by A31aH and the acid dissociation constant a1-4 derived from the acidic site represented by A31bH. Furthermore, the acid dissociation constants a1-3 and a1-4 are equivalent to the aforementioned acid dissociation constant a1. Furthermore, A31a- and A32- can be the same or different. Also, M31a+, M31b+, and M32+ can be the same or different. At least one of M31a+, M31b+, M32+, A31a-, A32-, L31 and L32 may have an acid-degradable group as a substituent.

[0167] In equation (Ia-4), A41a-, A41b-, and A42- each independently represent a monovalent anionic functional group. Furthermore, the definitions of monovalent anionic functional groups represented by A41a- and A41b- are synonymous with A21a- and A21b- in equation (Ia-2) above. The definition of a monovalent anionic functional group represented by A42- is synonymous with A32- in equation (Ia-3) above, and the preferred form is also the same. M41a+, M41b+, and M42+ each independently represent an organic cation. L 41 represents a trivalent organic group.

[0168] In formula (Ia-4) above, in compound PNIa-4 formed by replacing the organic cations represented by M 41a+, M 41b+, and M 42+ with H+, the acid dissociation constant a2 derived from the acidic site represented by A 42H is greater than the acid dissociation constants a1-5 derived from the acidic site represented by A 41aH and a1-6 derived from the acidic site represented by A 41bH. Furthermore, the acid dissociation constants a1-5 and a1-6 are equivalent to the aforementioned acid dissociation constant a1. Furthermore, A41a-, A41b-, and A42- can be the same or different from each other. Also, M41a+, M41b+, and M42+ can be the same or different from each other. At least one of M 41a+, M 41b+, M 42+, A 41a-, A 41b-, A 42- and L 41 may have an acid-degradable group as a substituent.

[0169] There are no particular limitations on the divalent organic groups represented by L 21 and L 22 in formula (Ia-2) and L 31 and L 32 in formula (Ia-3). Examples include -CO-, -NR-, -O-, -S-, -SO-, and -SO-. 2- Alkyl groups (preferably with 1 to 6 carbon atoms, and can be straight-chain or branched), cycloalkyl groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic hydrocarbon cyclocyclic groups (preferably 6 to 10-membered rings, and even more preferably 6-membered rings), and divalent organogroups formed by combining a plurality of these. The R in -NR- above can be a hydrogen atom or a monovalent organogroup. There are no particular limitations on the monovalent organic group; for example, it is preferably an alkyl group (preferably having 1 to 6 carbon atoms). The aforementioned alkyl groups, cycloalkyl groups, alkenyl groups, divalent aliphatic heterocyclic groups, divalent aromatic heterocyclic groups, and divalent aromatic hydrocarbon cyclocyclic groups may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0170] The divalent organic groups represented by L 21 and L 22 in formula (Ia-2) and L 31 and L 32 in formula (Ia-3), for example, are also preferably divalent organic groups represented by the following formula (L2).

[0171] [Chemical Formula 27]

[0172] In equation (L2), q represents an integer from 1 to 3. * indicates the bond position. Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. As for the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, it is even more preferably that Xf in both cases is a fluorine atom.

[0173] LA represents a single-bonded or divalent linker. There are no particular limitations on the divalent linker represented by LA. Examples include -CO-, -O-, -SO-, -SO 2-, alkyl groups (preferably with 1 to 6 carbons, which can be straight-chain or branched), cycloalkyl groups (preferably with 3 to 15 carbons), divalent aromatic hydrocarbon cycloalkanes (preferably 6 to 10-membered rings, more preferably 6-membered rings), and divalent linkers formed by combining a plurality of these. The aforementioned alkyl groups, cycloalkyl groups, and divalent aromatic hydrocarbon cyclogroups may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0174] Examples of divalent organic groups represented by formula (L2) include *-CF 2-*, *-CF 2-CF 2-*, *-CF 2-CF 2-CF 2-*, *-Ph-O-SO 2-CF 2-*, *-Ph-O-SO 2-CF 2-CF 2-*, *-Ph-O-SO 2-CF 2-CF 2-*, and *-Ph-OCO-CF 2-*. Furthermore, the so-called Ph-system can be a substituted phenyl group, preferably 1,4-phenyl. There are no particular limitations on the substituents, but they are preferably alkyl (e.g., preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), alkoxy (e.g., preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or alkoxycarbonyl (e.g., preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms). When L 21 and L 22 in formula (Ia-2) represent divalent organic groups represented by formula (L2), the bond (*) on the LA side in formula (L2) is preferably bonded to A 21a- and A 21b- in formula (Ia-2). When L 31 and L 32 in formula (Ia-3) represent divalent organic groups represented by formula (L2), the bond (*) on the LA side in formula (L2) is preferably bonded to A 31a- and A 32- in formula (Ia-3).

[0175] -Compounds represented by formula (Ia-5)- Next, equation (Ia-5) will be explained.

[0176] [Chemical Formula 28]

[0177] In formula (Ia-5), A51a-, A51b-, and A51c- each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional group represented by A51a-, A51b-, and A51c- refers to a monovalent group containing the aforementioned anionic site A1-. There is no particular limitation on the monovalent anionic functional group represented by A51a-, A51b-, and A51c-; for example, monovalent anionic functional groups selected from the group consisting of formulas (AX-1) to (AX-3) can be cited. A 52a- and A 52b- represent divalent anionic functional groups. Here, the divalent anionic functional groups represented by A 52a- and A 52b- refer to divalent linking groups containing the aforementioned anionic site A 2-. For example, divalent anionic functional groups selected from the group consisting of the above-described formulas (BX-8) to (BX-11) can be cited as examples of divalent anionic functional groups represented by A 22-.

[0178] M51a+, M51b+, M51c+, M52a+, and M52b+ each independently represent an organic cation. At least one of M51a+, M51b+, M51c+, M52a+, and M52b+ is the specific cation mentioned above. L51 and L53 each independently represent a divalent organogroup. The divalent organogroups represented by L51 and L53 are synonymous with L21 and L22 in the above formula (Ia-2), and are also the same in preferred form. L 52 represents a trivalent organogroup. As a trivalent organogroup represented by L 52, it is synonymous with L 41 in the above formula (Ia-4), and the preferred form is also the same.

[0179] In the above formula (Ia-5), in the compound PNIa-5 formed by replacing the organic cations represented by M51a+, M51b+, M51c+, M52a+, and M52b+ with H+, the acid dissociation constants a2-1 and a2-2 of the acidic site represented by A52aH are greater than the acid dissociation constants a1-1, a1-2, and a1-3 of the acidic site represented by A51cH. Furthermore, acid dissociation constants a1-1 to a1-3 are equivalent to the aforementioned acid dissociation constant a1, and acid dissociation constants a2-1 and a2-2 are equivalent to the aforementioned acid dissociation constant a2. Furthermore, A 51a-, A 51b-, and A 51c- can be the same or different. Also, A 52a- and A 52b- can be the same or different. M 51a+, M 51b+, M 51c+, M 52a+, and M 52b+ can be the same or different. At least one of M 51b+, M 51c+, M 52a+, M 52b+, A 51a-, A 51b-, A 51c-, L 51, L 52 and L 53 may have an acid-degradable group as a substituent.

[0180] (Compound (NII)) The compound (NII) is a compound having two or more of the above-described structural sites X and one or more of the above-described structural sites Z, and is a compound that produces an acid comprising two or more first acidic sites derived from the above-described structural sites X and the above-described structural sites Z by irradiation with photochemical rays or radiation. Structural site Z: The site that can neutralize the nonionic nature of acids.

[0181] In compound (NII), the definitions of structural site X, A1- and M1+ are synonymous with the definitions of structural site X, A1- and M1+ in compound (NI) above, and are also the same in preferred form.

[0182] In the above-mentioned compound (NII), in the compound PNII formed by replacing the above-mentioned cation M1+ in the above-mentioned structural site X with H+, the preferred range of the acid dissociation constant a1 derived from the acidic site represented by HA1, formed by replacing the above-mentioned cation M1+ in the above-mentioned structural site X with H+, is the same as the acid dissociation constant a1 in the above-mentioned compound PNI. Furthermore, for example, when compound (NII) is a compound that produces an acid having two acidic sites derived from the aforementioned structural site X and the aforementioned structural site Z, compound PNII is equivalent to "a compound having two HA 1s". Having determined the acid dissociation constant of compound PNII, the acid dissociation constant when compound PNII is "a compound having one Al- and one HA 1" and the acid dissociation constant when "a compound having one Al- and one HA 1" becomes "a compound having two Al-" are equivalent to the acid dissociation constant a1.

[0183] The acid dissociation constant a1 can be determined using the method described above for determining the acid dissociation constant. The aforementioned compound PNII is equivalent to the acid produced when compound (NII) is irradiated with photochemical rays or radiation. Furthermore, the two or more structural parts X mentioned above may be the same or different. Similarly, the two or more A1- and the two or more M1+ mentioned above may be the same or different.

[0184] There are no particular limitations on the nonionicity of the acid in structural site Z, but it is preferable to have a site containing a group that can electrostatically interact with a proton or a functional group with electrons. Examples of functional groups capable of electrostatic interaction with protons or possessing electrons include, for instance, functional groups with macrocyclic structures such as cyclic polyethers, or functional groups containing nitrogen atoms with non-shared electron pairs that do not contribute to π-conjugation. Nitrogen atoms with non-shared electron pairs that do not contribute to π-conjugation refer, for example, nitrogen atoms having a partial structure as shown in the following formula.

[0185] [Chemical Formula 29]

[0186] Examples of partial structures that are functional groups capable of electrostatically interacting with protons or having electrons include crown ether structures, azacrown ether structures, first- to third-order amine structures, pyridine structures, imidazole structures, and pyrazine structures, with first- to third-order amine structures being preferred.

[0187] There are no particular limitations on the compound (NII), for example, compounds represented by the following formula (IIa-1) and the following formula (IIa-2) can be cited.

[0188] [Chemical Formula 30]

[0189] In equation (IIa-1) above, A61a- and A61b- are synonyms of A11- in equation (Ia-1) above, and the preferred state is also the same. Furthermore, M61a+ and M61b+ are synonyms of M11+ in equation (Ia-1) above, and the preferred state is also the same. In the above formula (IIa-1), L 61 and L 62 are synonyms with L 1 in the above formula (Ia-1), and the better state is also the same.

[0190] In formula (IIa-1), R2X represents a monovalent organogroup. There are no particular limitations on the monovalent organogroup represented by R2X; examples include alkyl groups (preferably with 1 to 10 carbon atoms, and can be linear or branched), cycloalkyl groups (preferably with 3 to 15 carbon atoms), or alkenyl groups (preferably with 2 to 6 carbon atoms). The -CH2- group contained in the alkyl, cycloalkyl, and alkenyl groups represented by R2X can be substituted by one or more combinations selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-. The aforementioned alkyl, cycloalkyl, and alkenyl groups may have substituents. There are no particular limitations on the substituents; for example, halogen atoms (preferably fluorine atoms) can be included.

[0191] In the above formula (IIa-1), in the compound PNIIa-1 formed by replacing the organic cations represented by M 61a+ and M 61b+ with H+, the acid dissociation constants a1-7 derived from the acidic site represented by A 61aH and a1-8 derived from the acidic site represented by A 61bH are equivalent to the above-mentioned acid dissociation constant a1. Furthermore, the compound PNIIa-1, formed by replacing the cation sites M61a+ and M61b+ in the above structural site X with H+ in formula (IIa-1), is equivalent to HA61a-L61-N(R2X)-L62-A61bH. Also, compound PNIIa-1 is the same acid produced from the compound represented by formula (IIa-1) by irradiation with photochemical rays or radiation. At least one of M 61a+, M 61b+, A 61a-, A 61b-, L 61, L 62 and R 2X may have an acid-degradable group as a substituent.

[0192] In equation (IIa-2) above, A71a-, A71b-, and A71c- are synonyms of A11- in equation (Ia-1) above, and their preferred states are also the same. M71a+, M71b+, and M71c+ are synonyms of M11+ in equation (Ia-1) above, and their preferred states are also the same. In the above formula (IIa-2), L 71, L 72 and L 73 are synonyms with L 1 in the above formula (Ia-1), and the better state is also the same.

[0193] In the above formula (IIa-2), in the compound PNIIa-2 formed by replacing the organic cations represented by M 71a+, M 71b+ and M 71c+ with H+, the acid dissociation constants a1-9, a1-10, and a1-11 of the acidic site represented by A 71aH are equivalent to the above-mentioned acid dissociation constant a1. Furthermore, in the above formula (IIa-1), the compound PNIIa-2, formed by replacing the above-mentioned cation sites M71a+, M71b+, and M71c+ in the above-mentioned structural site X with H+, is equivalent to HA71a-L71-N(L73-A71cH)-L72-A71bH. Also, compound PNIIa-2 is the same acid produced from the compound represented by formula (IIa-2) by irradiation with photochemical rays or radiation. At least one of M 71a+, M 71b+, M 71c+, A 71a-, A 71b-, A 71c-, L 71, L 72 and L 73 may have an acid-degradable group as a substituent.

[0194] Examples of sites other than cations that compounds (NI) and (NII) may have.

[0195] [Chemical Formula 31]

[0196] [Chemical Formula 32]

[0197] In the composition of this invention, compound (N) may be used alone or in combination with two or more.

[0198] The content of compound (N) in the composition of this invention is not particularly limited. For example, when compound (N) is used as a photoacid generator, the content of compound (N) in the composition of the present invention is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, relative to the total solid content of the composition of the present invention. The content of compound (N) in the composition of the present invention is preferably 55.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the composition of the present invention. For example, when compound (N) is used as an acid diffusion control agent, the content of compound (N) in the composition of the present invention is preferably 0.1 to 15.0% by mass, more preferably 1.0 to 15.0% by mass or more, relative to the total solid content of the composition of the present invention. Furthermore, for example, when compound (N) also functions as resin (A) whose polarity increases due to decomposition by the action of acid, the content of compound (N) in the composition of the present invention is preferably 40.0 to 99.9% by mass, and more preferably 60.0 to 98.0% by mass, relative to the total solid content of the composition of the present invention.

[0199] <Resin whose polarity increases due to the action of acid (A)> The following will describe resin (A) (also referred to as "resin (A)") whose polarity increases due to the action of acid. Resin (A) is an acid-degradable resin. Resin (A) typically contains groups that increase in polarity upon decomposition by the action of acid (also known as "acid-decomposable groups"), and preferably contains repeating units containing acid-decomposable groups. When resin (A) contains acid-decomposable groups, in the pattern forming method described in this specification, typically, when an alkaline developer is used as the developer, a positive pattern can be formed more preferably, and when an organic developer is used as the developer, a negative pattern can be formed more preferably. As a repeating unit having an acid-decomposable group, in addition to the repeating units having an acid-decomposable group described later, it is preferred to have a repeating unit having an acid-decomposable group containing an unsaturated bond.

[0200] (Repeating unit with acid-decomposing groups) Acid-degradable groups are groups that decompose to produce polar groups under the action of acid. Preferably, acid-degradable groups have a structure that protects the polar groups with groups that can be released by acid (release groups). That is, resin (A) has repeating units, and these repeating units have groups that decompose to produce polar groups under the action of acid. Resins with these repeating units exhibit increased polarity under the action of acid, thereby increasing their solubility relative to alkaline developers and decreasing their solubility relative to organic solvents. As a polar group, it is preferably a base-soluble group, such as carboxyl, phenolic hydroxyl, fluorinated alcohol, sulfonic acid, phosphoric acid, sulfonamide, sulfonimide, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene, as well as alcoholic hydroxyl groups. Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

[0201] As a group that is released by the action of an acid, for example, groups represented by formulas (Y1) to (Y4) can be cited. Equation (Y1): -C(Rx 1)(Rx 2)(Rx 3) Formula (Y2):-C(=O)OC(Rx 1)(Rx 2)(Rx 3) Equation (Y3): -C(R 36)(R 37)(OR 38) Equation (Y4): -C(Rn)(H)(Ar)

[0202] In formulas (Y1) and (Y2), Rx1 to Rx3 independently represent alkyl (straight-chain or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (straight-chain or branched), or aryl (monocyclic or polycyclic). Furthermore, when all Rx1 to Rx3 are alkyl (straight-chain or branched), at least two of Rx1 to Rx3 are preferably methyl. Wherein, Rx 1 to Rx 3 are each independently, preferably representing a straight-chain or branched alkyl group, and Rx 1 to Rx 3 are each independently, more preferably representing a straight-chain alkyl group. Two of Rx 1 to Rx 3 can be bonded together to form a single ring or multiple rings. The alkyl group of Rx 1 to Rx 3 is preferably an alkyl group with 1 to 5 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. As for the cycloalkyl groups Rx 1 to Rx 3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. The aryl group of Rx 1 to Rx 3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene. The alkenyl group of Rx1 to Rx3 is preferably vinyl. The ring formed by the two bonds in Rx 1 to Rx 3 is preferably a cycloalkyl group. The cycloalkyl group formed by the two bonds in Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl or adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms. A cycloalkyl group formed by two bonds in Rx1 to Rx3, wherein one of the methylene groups constituting the ring can be replaced by a heteroatom such as an oxygen atom, a heteroatom-containing group such as a carbonyl group, or a vinylene. In these cycloalkyl groups, one or more ethyl groups constituting the cycloalkane ring can be replaced by vinylenes. The group represented by formula (Y1) or formula (Y2) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl state. The photosensitive or radiosensitive linear resin composition, for example, in the case of a photoresist composition for EUV exposure, is formed by an alkyl group, cycloalkyl group, alkenyl group, aryl group, and two bonds of Rx1 to Rx3, and preferably has fluorine or iodine atoms as substituents.

[0203] In formula (Y3), R36 to R38 independently represent a hydrogen atom or a monovalent organogroup. R37 and R38 can bond together to form a ring. Examples of monovalent organogroups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R36 is preferably a hydrogen atom. Furthermore, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups may contain heteroatoms such as oxygen atoms and / or groups containing heteroatoms such as carbonyl groups. For example, in the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups, one or more methylene groups may be substituted by heteroatoms such as oxygen atoms and / or groups containing heteroatoms such as carbonyl groups. R 38 can bond with another substituent in the main chain of the repeating unit to form a ring. The group formed by R 38 bonding with another substituent in the main chain of the repeating unit is preferably a methylene isoalkyl group. In the case of photosensitive or radiosensitive linear resin compositions, such as photoresist compositions for EUV exposure, the monovalent organic groups represented by R 36 to R 38 and the ring formed by the mutual bonding of R 37 and R 38 are preferably further substituents of fluorine or iodine atoms.

[0204] As for formula (Y3), it is preferred to be a group represented by the following formula (Y3-1).

[0205] [Chemical Formula 33]

[0206] Here, L1 and L2 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, or groups formed by combining these (e.g., groups formed by combining alkyl and aryl). M represents a single-bonded or divalent linker. Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group composed of these (e.g., a group composed of alkyl and cycloalkyl groups). Alkyl and cycloalkyl groups, for example, in which one methylene group may be replaced by a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. Furthermore, it is preferable that one of L1 and L2 is a hydrogen atom, and the other is an alkyl, cycloalkyl, aryl, or a group composed of alkyl and aryl groups. At least two of Q, M, and L1 can be bonded to form a loop (preferably a 5- or 6-membered loop). From the viewpoint of pattern miniaturization, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl, while examples of tertiary alkyl groups include tributyl and adamantyl. In this isostate sample, the glass transition temperature (Tg) and activation energy are increased, thus ensuring film strength and suppressing fogging.

[0207] In photosensitive or radiosensitive linear resin compositions, such as photoresist compositions for EUV exposure, the alkyl, cycloalkyl, aryl, and groups combined therefrom represented by L1 and L2 are preferably substituents containing fluorine or iodine atoms. Preferably, the alkyl, cycloalkyl, aryl, and aralkyl groups contain heteroatoms such as oxygen atoms in addition to fluorine and iodine atoms. Specifically, for example, a methylene group may be substituted with a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group. In photosensitive or radiosensitive linear resin compositions, such as photoresist compositions for EUV exposure, the heteroatom is preferably selected from the group consisting of alkyl groups containing heteroatoms represented by Q, cycloalkyl groups containing heteroatoms, aryl groups, amino groups, ammonium groups, mercapto groups, cyano groups, aldehyde groups, and groups composed of combinations thereof.

[0208] In formula (Y4), Ar represents an aromatic cycloalkyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond together to form a non-aromatic ring. Ar is preferably an aryl group. In photosensitive or radiosensitive linear resin compositions, such as photoresist compositions for EUV exposure, the aromatic cycloalloy represented by Ar and the alkyl, cycloalkyl and aryl groups represented by Rn are preferably substituents having fluorine or iodine atoms.

[0209] From the viewpoint of excellent acid decomposition properties of repeating units, in the release group protecting the polar group, when the non-aromatic ring is directly bonded to the polar group (or its residue), the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) in the non-aromatic ring is preferably not a halogen atom such as a fluorine atom as a substituent.

[0210] In addition, the group that is removed by the action of acid can also be 2-cyclopentenyl with a substituent (alkyl, etc.) such as 3-methyl-2-cyclopentenyl, and cyclohexyl with a substituent (alkyl, etc.) such as 1,1,4,4-tetramethylcyclohexyl.

[0211] As a repeating unit with an acid-decomposable group, it is also preferred to be a repeating unit represented by formula (A).

[0212] [Chemical Formula 34]

[0213] L1 represents a divalent linker that may have a fluorine or iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine or iodine atom, or an aryl group that may have a fluorine or iodine atom; and R2 represents a detached group that can have a fluorine or iodine atom after being desorbed by an acid. At least one of L1, R1, and R2 has a fluorine or iodine atom. Examples of divalent linking groups represented by L1 that may have fluorine or iodine atoms include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that may have fluorine or iodine atoms (e.g., alkylene, cycloalkylene, alkenylene, and arylene), and linking groups formed by multiple such groups. Preferably, L1 is -CO-, arylene, or -arylene-alkylene-with fluorine or iodine atoms, and more preferably -CO-, or -arylene-alkylene-with fluorine or iodine atoms. As an enfrylene, enfrylene is preferred. The alkyl group can be linear or branched. There is no particular limitation on the number of carbon atoms in the alkyl group, but it is preferred to be 1 to 10, and more preferably 1 to 3. There is no particular limitation on the total number of fluorine and iodine atoms contained in the alkyl group having fluorine or iodine atoms, but it is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0214] The alkyl group represented by R1 can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in the alkyl group, but it is preferred to be 1 to 10, and more preferably 1 to 3. There is no particular limitation on the total number of fluorine and iodine atoms contained in the alkyl group represented by R1 that has fluorine or iodine atoms, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. Alkyl groups represented by R1 may contain heteroatoms such as oxygen atoms in addition to halogen atoms.

[0215] As a detaching radical represented by R 2, which may have fluorine or iodine atoms, examples can be given of detaching radicals represented by the above formulas (Y1) to (Y4) that have fluorine or iodine atoms.

[0216] As a repeating unit with an acid-decomposable group, it is preferably a repeating unit represented by formula (AI).

[0217] [Chemical Formula 35]

[0218] In formula (AI), Xa 1 represents a hydrogen atom or an alkyl group that may have substituents. T represents a single bond or a divalent linker. Rx 1 to Rx 3 independently represent alkyl (linear or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (linear or branched), or aryl (monocyclic or polycyclic). Wherein, when all Rx 1 to Rx 3 are alkyl (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl. Two of Rx 1 to Rx 3 can bond together to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0219] As represented by Xa 1, an alkyl group that may have substituents, examples include methyl or a group represented by -CH 2-R 11. R 11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organogroup. As a monovalent organogroup represented by R 11, examples include alkyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, acetyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, and alkoxy groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, preferably alkyl groups with 3 or fewer carbon atoms, and more preferably methyl groups. As Xa 1, a hydrogen atom, methyl, trifluoromethyl, or hydroxymethyl group is preferred.

[0220] Examples of divalent linking groups for T include alkyl groups, aromatic cycloyl groups, -COO-Rt- groups, and -O-Rt- groups. In these formulas, Rt represents an alkyl or cycloalkyl group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0221] The alkyl group of Rx 1 to Rx 3 is preferably an alkyl group with 1 to 4 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. As for the cycloalkyl groups Rx 1 to Rx 3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. The aryl group of Rx 1 to Rx 3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene. The alkenyl group of Rx1 to Rx3 is preferably vinyl. The cycloalkyl group formed by two bonds in Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. Also preferably, it is a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. Cycloalkyl groups formed by two bonds in Rx1 to Rx3, for example, in which one of the methylene groups constituting the ring can be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylene. Furthermore, in such cycloalkyl groups, one or more of the ethyl groups constituting the cycloalkane ring can be replaced by vinylene. The repeating unit represented by formula (AI), for example, preferably Rx 1 is methyl or ethyl, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl state.

[0222] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). Preferably, the substituent has 8 or fewer carbon atoms.

[0223] As the repeating unit represented by formula (AI), it is preferably an acid-degradable (meth)acrylate trialkyl ester repeating unit (Xa 1 represents a hydrogen atom or methyl group, and T represents a single bond repeating unit).

[0224] Specific examples of repeating units with acid-decomposing groups are shown below, but are not limited to these. Furthermore, in the formula, Xa1 represents H, CH3, CF3, or CH2OH, and Rxa and Rxb independently represent straight-chain or branched alkyl groups having 1 to 5 carbon atoms.

[0225] [Chemical Formula 36]

[0226] [Chemical Formula 37]

[0227] [Chemical Formula 38]

[0228] [Chemical Formula 39]

[0229] [Chemical Formula 40]

[0230] Resin (A), as a repeating unit with an acid-degradable group, may have repeating units containing an acid-degradable group with an unsaturated bond. As a repeating unit having an acid-decomposable group containing unsaturated bonds, it is preferably a repeating unit represented by formula (B).

[0231] [Chemical Formula 41]

[0232] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group that may have substituents. L represents a single bond or a divalent linker that may have substituents. Ry 1 to Ry 3 independently represent a straight-chain or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. At least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry 1 to Ry 3 can bond together to form a monocyclic or polycyclic ring (monocyclic or polycyclic cycloalkyl, cycloalkenyl, etc.).

[0233] As represented by Xb, an alkyl group that can have substituents, examples include groups represented by methyl or -CH2-R11. R11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, for example, an alkyl group with 5 or fewer carbon atoms that can be substituted by a halogen atom, an alkoxy group with 5 or fewer carbon atoms that can be substituted by a halogen atom, and an alkoxy group with 5 or fewer carbon atoms that can be substituted by a halogen atom, preferably an alkyl group with 3 or fewer carbon atoms, and more preferably a methyl group. As Xb, a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group are preferred.

[0234] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In these formulas, Rt represents an alkyl group, an cycloalkyl group, or an aromatic cycloalkyl group, preferably an aromatic cycloalkyl group. The L group is preferably -Rt-, -CO-, -COO-Rt-CO-, or -Rt-CO-. Rt may have halogen atoms, hydroxyl groups, alkoxy groups, or other substituents.

[0235] The alkyl group of Ry 1 to Ry 3 is preferably an alkyl group with 1 to 4 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl. As for the cycloalkyl groups of Ry 1 to Ry 3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl. The aryl group of Ry 1 to Ry 3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene. The alkenyl group of Ry 1 to Ry 3 is preferably vinyl. The acetylenic group of Ry 1 to Ry 3 is preferably acetylenic. As the cycloalkenyl group of Ry 1 to Ry 3, it is preferably a structure containing a double bond in part of a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. The cycloalkyl group formed by two bonds in Ry 1 to Ry 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. More preferably, it is a monocyclic cycloalkyl group having 5 to 6 carbon atoms. Cycloalkyl or cycloalkenyl groups formed by two bonds in Ry 1 to Ry 3, for example, wherein one of the methylene groups constituting the ring can be replaced by a heteroatom such as an oxygen atom, a carbonyl group, a heteroatom-containing group such as -SO 2- or -SO 3-, vinylene, or a combination thereof. Furthermore, in these cycloalkyl or cycloalkenyl groups, one or more of the ethyl groups constituting the cycloalkane or cycloalkene ring can be replaced by vinylene. The repeating unit represented by formula (B), for example, preferably Ry 1 is methyl, ethyl, vinyl, allyl, or aryl, and Ry 2 and Ry 3 are bonded to form the above-mentioned cycloalkyl or cycloalkenyl state.

[0236] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). Preferably, the substituent has 8 or fewer carbon atoms.

[0237] As the repeating unit represented by formula (B), it is preferably an acid-degradable (meth)acrylic acid trialkyl ester repeating unit (Xb represents a hydrogen atom or methyl, and L represents a -CO- group repeating unit), an acid-degradable hydroxystyrene trialkyl ether repeating unit (Xb represents a hydrogen atom or methyl, and L represents a phenyl repeating unit), or an acid-degradable styrene carboxylic acid trialkyl ester repeating unit (Xb represents a hydrogen atom or methyl, and L represents a -Rt-CO- group (Rt is an aromatic group) repeating unit).

[0238] The content of repeating units containing acid-degradable groups with unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in resin (A). Furthermore, as an upper limit, it is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, relative to all repeating units in resin (A).

[0239] Specific examples of repeating units having acid-decomposing groups containing unsaturated bonds are shown below, but are not limited thereto. Furthermore, in the formula, Xb and L1 represent any of the substituents and linkers as described above, Ar represents an aromatic group, R represents a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acetoxy, cyano, nitro, amino, halogen atom, ester (-OCOR''' or -COOR''', R'''' is an alkyl or fluorinated alkyl with 1 to 20 carbon atoms), or a carboxyl group, etc., R' represents a straight-chain or branched alkyl, monocyclic or polycyclic cycloalkyl, alkenyl, alkynyl, or monocyclic or polycyclic aryl, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as -SO2- or -SO3-, vinylidene, or a combination thereof, and n, m, and l represent integers greater than or equal to 0.

[0240] [Chemical Formula 42]

[0241] [Chemical Formula 43]

[0242] [Chemical Formula 44]

[0243] [Chemical Formula 45]

[0244] The content of repeating units with acid-degradable groups, relative to all repeating units in resin (A), is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more. Furthermore, as an upper limit, relative to all repeating units in resin (A), it 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.

[0245] Resin (A) may contain at least one repeating unit selected from the group consisting of group A below and / or at least one repeating unit selected from the group consisting of group B below. Group A: A group consisting of repeating units of the following (20) to (25). (20) The repeating unit with acid groups, described later. (21) The repeating unit described later, which does not have any of the acid-decomposing groups or acid groups, but has a fluorine atom, a bromine atom, or an iodine atom. (22) Repeating units having lactone, sulcinolone, or carbonate groups, as described later. (23) The repeating unit with photoacid-generating group described later. (24) Repeating units described later, represented by equation (V-1) or equation (V-2) below. (25) Repeating units used to reduce the motion of the main chain Furthermore, the repeating units represented by equations (A) to (E) described later are equivalent to (25) repeating units used to reduce the mobility of the main chain. Group B: A group consisting of repeating units of the following (30) to (32). (30) The repeating unit described below, having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano, and base-soluble group. (31) The repeating unit described later, which has an alicyclic hydrocarbon structure and does not exhibit acid decomposition properties. (32) The repeating unit described later, which does not have either a hydroxyl or a cyano group, and is represented by formula (III).

[0246] Resin (A) preferably has acid groups, and as described below, it preferably contains repeating units with acid groups. Furthermore, the definition of acid groups will be explained later along with the preferred state of repeating units with acid groups. When resin (A) has acid groups, the interaction between resin (A) and the acid generated by the photoacid generator is more excellent. As a result, acid diffusion can be further suppressed, making the cross-sectional shape of the formed pattern closer to a rectangle.

[0247] Resin (A) may have at least one repeating unit selected from the group consisting of the above-mentioned group A. When a photosensitive radioactive or radiosensitive linear resin composition is used as a photosensitive radioactive or radiosensitive linear resin composition for EUV exposure, resin (A) preferably has at least one repeating unit selected from the group consisting of the above-mentioned group A. Resin (A) may contain at least one of fluorine atoms and iodine atoms. When the photosensitive or radiosensitive linear resin composition is used as a photosensitive or radiosensitive linear resin composition for EUV exposure, resin (A) preferably contains at least one of fluorine atoms and iodine atoms. When 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 have both repeating units containing fluorine atoms and repeating units containing iodine atoms. Resin (A) may have repeating units containing aromatic groups. When a photosensitive or radiosensitive linear resin composition is used as a photosensitive or radiosensitive linear resin composition for EUV exposure, resin (A) is preferably a repeating unit containing aromatic groups. Resin (A) may have at least one repeating unit selected from the group consisting of the above-described group B. When the photosensitive radioactive or radiosensitive linear resin composition is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, resin (A) preferably has at least one repeating unit selected from the group consisting of the above-described group B. Furthermore, when a photosensitive or radiosensitive linear resin composition is used as a photosensitive or radiosensitive linear resin composition for ArF, resin (A) is preferably free of either fluorine atoms or silicon atoms. When a photosensitive or radiosensitive linear resin composition is used as a photosensitive or radiosensitive linear resin composition for ArF, resin (A) is preferably free of aromatic groups.

[0248] (Repeating units with acid groups) Resin (A) may have repeating units containing acid groups. As an acid group, it is preferable to have an acid group with a pKa of 13 or less. The acid dissociation constant of the above-mentioned acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (A) contains acid groups with a pKa of 13 or less, the content of acid groups in resin (A) is not particularly limited, and is mostly 0.2 to 6.0 mmol / g. Preferably, it is 0.8 to 6.0 mmol / g, more preferably 1.2 to 5.0 mmol / g, and even more preferably 1.6 to 4.0 mmol / g. If the content of acid groups is within the above range, development will proceed well, resulting in excellent pattern shape and resolution. As an acid group, for example, it is preferably a carboxyl group, a phenolic hydroxyl group, a fluorool group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. In the aforementioned hexafluoroisopropanol group, one or more (preferably one to two) fluorine atoms can be substituted by groups other than fluorine atoms (alkoxycarbonyl groups, etc.). As an acid group, -C(CF3)(OH)-CF2- is also preferred. Furthermore, one or more fluorine atoms can be substituted by groups other than fluorine atoms to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acid group is preferably a repeating unit that is different from repeating units having a structure in which a polar group is protected by a group that is removed by the action of the acid described above, and repeating units having lactone, sulcinolone or carbonate groups as described later. Repeating units with acid groups can have fluorine or iodine atoms.

[0249] The following repeating units can be cited as examples of repeating units having acid groups.

[0250] [Chemical Formula 46]

[0251] As a repeating unit having an acid group, it is preferably a repeating unit represented by the following formula (1).

[0252] [Chemical Formula 47]

[0253] In formula (1), A represents a hydrogen atom, alkyl, cycloalkyl, halogen atom, or cyano. R represents a halogen atom, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, alkoxy, alkylcarbonyloxy, alkylsulfonoxy, alkoxycarbonyl, or aryloxycarbonyl, which may be the same or different when there are multiple Rs. When there are multiple Rs, they can form a ring together. R is preferably a hydrogen atom. a represents an integer from 1 to 3. b represents an integer from 0 to (5-a).

[0254] The following examples illustrate repeating units with acid groups. In the formula, a represents 1 or 2.

[0255] [Chemical Formula 48]

[0256] [Chemical Formula 49]

[0257] [Chemical Formula 50]

[0258] [Chemical Formula 51]

[0259] The content of repeating units with acid groups is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in resin (A). Furthermore, as an upper limit, it is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to all repeating units in resin (A).

[0260] (A repeating unit that does not have an acid-decomposing group or any of the acid groups, but has a fluorine atom, a bromine atom or an iodine atom) In addition to the aforementioned <repeating units with acid-decomposable groups> and <repeating units with acid groups>, resin (A) may also have repeating units (hereinafter also referred to as unit X) that do not have either acid-decomposable groups or acid groups but have fluorine, bromine, or iodine atoms. The <repeating units with fluorine, bromine, or iodine atoms that do not have either acid-decomposable groups or acid groups> are preferably different from other types of repeating units belonging to group A, such as <repeating units with lactone, sulopentalide, or carbonate groups> and <repeating units with photoacid-generating groups>, as described later.

[0261] As unit X, it is preferably a repeating unit represented by equation (C).

[0262] [Chemical Formula 52]

[0263] L 5 represents a single bond or an ester group. R 9 represents an alkyl group that may have a hydrogen atom, or a fluorine atom, or an iodine atom. R 10 represents an alkyl group that may have a hydrogen atom, a fluorine atom, or an iodine atom, a cycloalkyl group that may have a fluorine atom, or an aryl group that may have a fluorine atom, or an iodine atom, or a combination thereof.

[0264] The following are examples of repeating units having fluorine or iodine atoms.

[0265] [Chemical Formula 53]

[0266] The content of unit X, relative to all repeating units in resin (A), is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. Furthermore, as an upper limit, relative to all repeating units in resin (A), it is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less.

[0267] In the repeating units of resin (A), the total content of repeating units containing at least one of fluorine, bromine, and iodine atoms is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and especially preferably 40 mol% or more, relative to all repeating units of resin (A). There is no particular upper limit; for example, it may be 100 mol% or less relative to all repeating units of resin (A). Furthermore, as repeating units containing at least one of fluorine, bromine, and iodine atoms, examples include: repeating units having fluorine, bromine, or iodine atoms and having an acid-decomposing group; repeating units having fluorine, bromine, or iodine atoms and having an acid group; and repeating units having fluorine, bromine, or iodine atoms.

[0268] (Repeating units with lactone, sulcinolone, or carbonate groups) Resin (A) may have a repeating unit (hereinafter also referred to as "unit Y") containing at least one of the group consisting of lactone groups, sulcinolone groups and carbonate groups. Unit Y is also preferably free of acid groups such as hydroxyl and hexafluoropropanol groups.

[0269] As a lactone group or sulfonolactone group, it is acceptable as long as it has a lactone structure or sulfonolactone structure. The lactone structure or sulfonolactone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sulfonolactone structure. More preferably, it is a structure in which other ring structures are formed by ring condensation on the 5-7 membered ring lactone structure in the form of a bicyclic or spirocyclic structure, or a structure in which other ring structures are formed by ring condensation on the 5-7 membered ring sulfonolactone structure in the form of a bicyclic or spirocyclic structure. Resin (A) preferably has repeating units containing lactone or sulfonyl groups, which are formed by removing one or more hydrogen atoms from the ring-member atoms of a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21), or a sulfonyl structure represented by any one of the following formulas (SL1-1) to (SL1-3). The lactone or sulfonyl groups can be directly bonded to the main chain. For example, the ring-member atoms of the lactone or sulfonyl groups can also constitute the main chain of resin (A).

[0270] [Chemical Formula 54]

[0271] The aforementioned lactone or sulopentalide structures can also have substituents (Rb 2). Preferred substituents (Rb 2) include alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 4 to 7 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 1 to 8 carbon atoms, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. n 2 represents an integer from 0 to 4. When n 2 is 2 or more, the plurality of Rb 2 groups can be different, and the plurality of Rb 2 groups can also bond together to form a ring.

[0272] As a repeating unit having a group containing a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sulfonyl lactone structure represented by any one of formulas (SL1-1) to (SL1-3), for example, a repeating unit represented by the following formula (AI) can be cited.

[0273] [Chemical Formula 55]

[0274] In formula (AI), Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that can be present in the alkyl group of Rb 0 include hydroxyl groups and halogen atoms. Examples of halogen atoms that can be represented by Rb 0 include fluorine, chlorine, bromine, and iodine. Rb 0 is preferably represented by hydrogen or methyl. Ab represents a single bond, an alkyl group, a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linker formed by combining these. Preferably, Ab is a single bond or a linker represented by -Ab 1-CO 2-. Ab 1 is a straight-chain or branched alkyl group, or a monocyclic or polycyclic cycloalkyl group, preferably methylene, ethyl, cyclohexyl, adamantyl, or norbornyl. V represents a group formed by removing a hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), or a group formed by removing a hydrogen atom from a ring member atom of a sulfonyl lactone structure represented by any one of formulas (SL1-1) to (SL1-3).

[0275] When an optical isomer exists in a repeating unit having a lactone group or a sulcinolone group, any one of the optical isomers can be used. Furthermore, a single optical isomer can be used alone, or multiple optical isomers can be used in combination. When primarily using one optical isomer, its optical purity (ee) is preferably 90% or higher, and more preferably 95% or higher.

[0276] As a carbonate group, a cyclic carbonate group is preferred. As a repeating unit having a cyclic carbonate group, it is preferably a repeating unit represented by the following formula (A-1).

[0277] [Chemical Formula 56]

[0278] In formula (A-1), RA1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably methyl). n represents an integer greater than or equal to 0. RA2 represents a substituent. When n is 2 or more, there may be multiple RA2 groups, which may be identical or different. A represents a single bond or a divalent linking group. As the aforementioned divalent linking group, it is preferably an alkyl 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 linking group formed by combining these. Z represents a group that forms a monocyclic or polycyclic atom together with the group represented by -O-CO-O- in the formula.

[0279] The following example illustrates unit Y. In the formula, Rx represents a hydrogen atom, -CH3, -CH2OH, or -CF3.

[0280] [Chemical Formula 57]

[0281] [Chemical Formula 58] (In the formula, Rx represents H, CH3, CH2OH, or CF3)

[0282] [Chemical Formula 59] (In the formula, Rx represents H, CH3, CH2OH, or CF3)

[0283] The content of unit Y, relative to all repeating units in resin (A), is preferably 1 mol% or more, more preferably 10 mol% or more. Furthermore, as an upper limit, relative to all repeating units in resin (A), it is preferably 85 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and especially preferably 60 mol% or less.

[0284] (Repeating unit with photoacid-generating group) As a repeating unit other than those mentioned above, resin (A) may have repeating units containing groups that generate acid by irradiation with photochemical rays or radiation (hereinafter also referred to as "photoacid-generating groups"). As a repeating unit containing a photoacid generating group, the repeating unit represented by equation (4) can be cited.

[0285] [Chemical Formula 60]

[0286] R 41 represents a hydrogen atom or a methyl group. L 41 represents a single bond or a divalent linker. L 42 represents a divalent linker. R 40 represents a structural site where acid is generated in the side chain due to decomposition by photochemical irradiation or radiation. As described above, in the state in which compound (N) also functions as a resin (A) whose polarity increases due to decomposition by acid action, resin (A) preferably has a repeating unit containing a photoacid-generating group, and the cation contained in the photoacid-generating group is a cation represented by the general formula (N1). In such a state, photosensitive or radiosensitive linear resin compositions may additionally contain resin (A), but it is also preferred that they do not contain resin (A). The following are examples of repeating units having photoacid-generating groups.

[0287] [Chemical Formula 61]

[0288] Furthermore, as a repeating unit represented by equation (4), examples can be found in paragraphs

[0094] to

[0105] of Japanese Patent Application Publication No. 2014-041327 and paragraph

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

[0289] The content of repeating units having photoacid-generating groups is preferably 1 mol% or more, more preferably 5 mol% or more, relative to all repeating units in resin (A). Furthermore, as an upper limit, it is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, relative to all repeating units in resin (A).

[0290] (Repeating units represented by equation (V-1) or equation (V-2) below) Resin (A) may have repeating units represented by the following formula (V-1) or the following formula (V-2). The repeating unit represented by the following formula (V-1) and the following formula (V-2) is preferably a repeating unit that is different from the repeating unit described above.

[0291] [Chemical Formula 62]

[0292] In the formula, R6 and R7 independently represent a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acetoxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR or -COOR: R is an alkyl group or fluorinated alkyl group with 1 to 6 carbon atoms), or carboxyl group. As an alkyl group, it is preferred to be a straight-chain, branched, or cyclic alkyl group with 1 to 10 carbon atoms. n 3 represents an integer from 0 to 6. n 4 represents an integer from 0 to 4. X 4 represents a methylene group, an oxygen atom, or a sulfur atom. The following examples illustrate repeating units represented by equations (V-1) or (V-2). As a repeating unit represented by formula (V-1) or (V-2), for example, the repeating unit described in paragraph

[0100] of International Publication No. 2018 / 193954 can be cited.

[0293] (Repetitive units used to reduce the mobility of the main chain) From the viewpoint of suppressing excessive diffusion of the generated acid or pattern collapse during development, resin (A) preferably has a high glass transition temperature (Tg). Tg is preferably greater than 90°C, more preferably greater than 100°C, further preferably greater than 110°C, and most preferably greater than 125°C. Furthermore, from the viewpoint of having a good dissolution rate in the developer, Tg is preferably below 400°C, and more preferably below 350°C. Furthermore, in this specification, the glass transition temperature (Tg) of polymers such as resin (A) (hereinafter also referred to as "Tg of repeating unit") is calculated by the following method. First, the Tg of the homopolymer consisting only of each repeating unit contained in the polymer is calculated separately using the Bicerano method. Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Then, the Tg at each mass ratio is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed to obtain the Tg (°C) of the polymer. The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). When calculating Tg using the Bicerano method, the polymer physical property assessment software MDL Polymer (MDL Information Systems, Inc.) can be used.

[0294] To increase the Tg of resin (A) (preferably, to make Tg exceed 90°C), it is preferable to reduce the mobility of the main chain of resin (A). Methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e). (a) Introducing large-volume substituents into the main chain (b) Introducing multiple substituents into the main chain (c) Introducing substituents near the main chain to induce interactions between resins (A). (d) Formation of the main chain in the ring structure (e) Linking ring structures to the main chain In addition, resin (A) is preferably a repeating unit having a Tg of 130°C or higher from homopolymer. Furthermore, there are no particular restrictions on the types of repeating units whose Tg of the homopolymer is above 130°C, as long as the repeating unit whose Tg of the homopolymer is above 130°C as calculated using the Bicerano method is acceptable. In addition, the repeating units represented by equations (A) to (E) described later, depending on the type of functional groups therein, are equivalent to repeating units whose Tg of the homopolymer is above 130°C.

[0295] As one example of a specific implementation of (a) above, a method of introducing a repeating unit represented by formula (A) into resin (A) can be cited.

[0296] [Chemical Formula 63]

[0297] In formula (A), RA represents a group containing a polycyclic structure. Rx represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, and these multiple ring structures may or may not be fused. As a specific example of a repeating unit represented by formula (A), the repeating unit described in paragraphs

[0107] to

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

[0298] As one example of a specific implementation of (b) above, a method of introducing repeating units represented by formula (B) into resin (A) can be cited.

[0299] [Chemical Formula 64]

[0300] In formula (B), Rb1 to Rb4 independently represent hydrogen atoms or organic groups, and at least two of Rb1 to Rb4 represent organic groups. There are no particular restrictions on the types of other organic groups if at least one of the organic groups is a group that is directly linked to the main chain of the repeating unit in the ring structure. Furthermore, if none of the organic groups are directly linked to the main chain of the ring structure and repeating unit, then at least two of the organic groups are substituents with a number of three or more constituent atoms other than hydrogen atoms. As a specific example of a repeating unit represented by equation (B), the repeating unit described in paragraphs

[0113] to

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

[0301] As one example of a specific implementation of (c) above, a method of introducing a repeating unit represented by formula (C) into resin (A) can be cited.

[0302] [Chemical Formula 65]

[0303] In formula (C), Rc1 to Rc4 independently represent hydrogen atoms or organic groups, and at least one of Rc1 to Rc4 is a group containing hydrogen atoms with hydrogen bonding in the main chain carbon up to 3 atoms. Preferably, for inducing the interaction between the main chains of resin (A), hydrogen atoms with hydrogen bonding in the main chain up to 2 atoms (closer to the main chain side) are preferred. As a specific example of a repeating unit represented by formula (C), the repeating unit described in paragraphs

[0119] to

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

[0304] As one example of a specific implementation of (d) above, a method of introducing a repeating unit represented by formula (D) into resin (A) can be cited.

[0305] [Chemical Formula 66]

[0306] In formula (D), "Cyclic" represents a group whose main chain is formed in a cyclic structure. There is no particular restriction on the number of atoms constituting the ring. As a specific example of a repeating unit represented by formula (D), the repeating unit described in paragraphs

[0126] to

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

[0307] As one example of a specific implementation of (e) above, a method of introducing a repeating unit represented by formula (E) into resin (A) can be cited.

[0308] [Chemical Formula 67]

[0309] In formula (E), Re independently represents either a hydrogen atom or an organic group. Examples of organic groups that can have substituents include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. "Cyclic" refers to a cyclic group containing carbon atoms in the main chain. There is no particular limitation on the number of atoms contained in a cyclic group. As a specific example of a repeating unit represented by formula (E), the repeating unit described in paragraphs

[0131] to

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

[0310] (A repeating unit having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano, and base-soluble groups) Resin (A) may have repeating units containing at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano and base-soluble groups. As for the repeating units containing lactone, sulfonyl, or carbonate groups in resin (A), examples include the repeating units described in the above-mentioned <Repeating Units Containing Lactone, Sulfolactone, or Carbonate Groups>. A preferred content is also as described in the above-mentioned <Repeating Units Containing Lactone, Sulfolactone, or Carbonate Groups>.

[0311] Resin (A) may have repeating units containing hydroxyl or cyano groups. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl or cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl or cyano group. The repeating unit having a hydroxyl or cyano group is preferably free of acid-degradable groups. Examples of repeating units having a hydroxyl or cyano group include those described in paragraphs

[0081] to

[0084] of Japanese Patent Application Publication No. 2014-098921.

[0312] Resin (A) may have repeating units containing base-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonimide groups, disulfonimide groups, and aliphatic alcohol groups substituted with electron-withdrawing groups at the α-position (e.g., hexafluoroisopropanol groups), with carboxyl groups being preferred. By including repeating units with alkali-soluble groups in the resin (A), resolution in contact hole applications can be increased. Examples of repeating units with alkali-soluble groups include those described in paragraphs

[0085] and

[0086] of Japanese Patent Application Publication No. 2014-098921.

[0313] (A repeating unit with an alicyclic hydrocarbon structure that does not exhibit acid decomposition properties) Resin (A) can have repeating units with an alicyclic hydrocarbon structure that do not exhibit acid decomposition properties. This reduces the leaching of low-molecular-weight components from the photoresist film into the immersion bath during immersion exposure. Examples of repeating units with an alicyclic hydrocarbon structure that do not exhibit acid decomposition properties include repeating units derived from 1-adamantane (meth)acrylate, diadamantane (meth)acrylate, tricyclodecyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0314] (A repeating unit represented by formula (III) that does not have either a hydroxyl or a cyano group) Resin (A) may have repeating units represented by formula (III) that do not have either hydroxyl or cyano groups.

[0315] [Chemical Formula 68]

[0316] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and not having either a hydroxyl or 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 a acetyl group. As a repeating unit represented by formula (III) that does not have either a hydroxyl or a cyano group, the repeating unit described in paragraphs

[0087] to

[0094] of Japanese Patent Application Publication No. 2014-098921 can be cited as an example.

[0317] (Other repeating units) In addition, resin (A) may have other repeating units besides the repeating units mentioned above. For example, resin (A) may have repeating units selected from the group consisting of repeating units having an oxathiane ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group.

[0318] In addition to the repeating units mentioned above, resin (A) may also have various repeating units to adjust dry etching resistance, standard developer compatibility, substrate adhesion, photoresist shape, resolution, heat resistance, and sensitivity.

[0319] As resin (A), particularly when the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, it is preferable that all repeating units are composed of repeating units derived from compounds having ethylene unsaturated bonds. In particular, it is also preferable that all repeating units are composed of (meth)acrylate repeating units. When all repeating units are composed of (meth)acrylate repeating units, it is permissible to use any of the following: all repeating units are methacrylate repeating units, all repeating units are acrylate repeating units, or all repeating units are composed of both methacrylate and acrylate repeating units. Preferably, the acrylate repeating units constitute 50 moles or less of all repeating units.

[0320] Resin (A) can be synthesized using conventional methods (such as free radical polymerization). Using the GPC method and converted to polystyrene, the weight-average molecular weight (Mw) of resin (A) is preferably below 30,000, and more preferably below 1,000. [~]30000, a further improvement is 3000. [~]30000, the best is 5000~15000. The dispersion (molecular weight distribution, Mw / Mn) of resin (A) is preferably 1 to 5, more preferably 1 to 3, further preferably 1.2 to 3.0, and especially preferably 1.2 to 2.0. The smaller the dispersion, the better the resolution and photoresist shape, and the smoother the sidewalls and the better the roughness of the photoresist pattern.

[0321] In the photosensitive or radiosensitive linear resin 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, relative to the total solid content of the photosensitive or radiosensitive linear resin composition. Resin (A) may be used in one or in combination with multiple types.

[0322] <Compounds that produce acids through exposure to photochemical rays or radiation (B)> In addition to the compound (N) mentioned above, the composition of the present invention may also contain a compound (B) that is different from compound (N) and produces acid by irradiation with photochemical rays or radiation (also referred to as compound (B) or "photoacid generator (B)"). The photoacid generator (B) can be in the form of a low molecular weight compound or in the form incorporated into a polymer (e.g., the resin (A) described later). Alternatively, it can be in both the form of a low molecular weight compound and the form incorporated into a polymer (e.g., the resin (A) described later). When the photoacid generator (B) is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular limitation on the lower limit, but it is preferably 100 or more. When the photoacid generator (B) is in the form of being incorporated into a part of the polymer, it can be incorporated into a part of the resin (A) or into a resin different from the resin (A). In this specification, the photoacid generator (B) is preferably in the form of a low molecular weight compound.

[0323] As a photoacid generator (B), for example, compounds represented by "M + X -" (onium salts) can be cited, preferably compounds that generate organic acids by exposure. Examples of the aforementioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acid, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonyl sulfonyl imine, bis(alkyl sulfonyl) imine, and tris(alkyl sulfonyl) methyl compounds.

[0324] In compounds denoted by "M +X -", M + represents an organic cation. There are no particular restrictions on whether an organic cation can be monovalent or divalent or higher. Among them, the organic cations mentioned above are preferably cations represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or cations represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0325] [Chemical Formula 69]

[0326] In the above formula (ZaI), R 201, R 202 and R 203 each independently represent an organic group. The number of carbon atoms in the organic groups of R 201, R 202, and R 203 is preferably 1 to 30, more preferably 1 to 20. Two of R 201 to R 203 can bond to form a ring structure, which may contain an oxygen atom, a sulfur atom, an ester group, an amino group, or a carbonyl group. Examples of groups formed by the bonding of two of R 201 to R 203 include, for example, alkyl groups (e.g., butyl and pentyl) and -CH 2-CH 2-O-CH 2-CH 2-.

[0327] Suitable examples of organic cations in formula (ZaI) include cations (ZaI-1), (ZaI-2), (ZaI-3b), and (ZaI-4b), which will be described later.

[0328] First, the cation (ZaI-1) will be explained. The cation (ZaI-1) is an aryl strontium cation, wherein at least one of R 201 to R 203 in the above formula (ZaI) is aryl. Aryl strontium cations can be composed of aryl groups from R201 to R203, or a portion of R201 to R203 can be aryl groups, with the remainder being alkyl or cycloalkyl groups. The ring structure can be formed by one of R 201 to R 203 being an aryl group and the remaining two bonds of R 201 to R 203, or it can contain an oxygen atom, a sulfur atom, an ester group, an amino group, or a carbonyl group within the ring. Examples of groups formed by the two bonds of R 201 to R 203 include alkyl groups (e.g., butyl, pentyl, and -CH 2-CH 2-O-CH 2-CH 2-), wherein one or more methylene groups can be substituted with an oxygen atom, a sulfur atom, an ester group, an amino group, and / or a carbonyl group. Examples of aryl strontium cations include triaryl strontium cations, diarylalkyl strontium cations, aryldialkyl strontium cations, diarylcycloalkyl strontium cations, and aryldicycloalkyl strontium cations.

[0329] The aryl group contained in the aryl strontium cation is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group can be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl strontium cation has two or more aryl groups, the two or more aryl groups can be the same or different. The aryl strontium cation may contain alkyl or cycloalkyl groups as desired, preferably straight-chain alkyl groups having 1 to 15 carbon atoms, branched alkyl groups having 3 to 15 carbon atoms, or cycloalkyl groups having 3 to 15 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, sec-butyl, tributyl, cyclopropyl, cyclobutyl, or cyclohexyl.

[0330] The substituents that may be present in the aryl, alkyl, and cycloalkyl groups of R 201 to R 203 are preferably alkyl (e.g., 1 to 15 carbons), cycloalkyl (e.g., 3 to 15 carbons), aryl (e.g., 6 to 14 carbons), alkoxy (e.g., 1 to 15 carbons), cycloalkylalkoxy (e.g., 1 to 15 carbons), halogen atoms (e.g., fluorine and iodine), hydroxyl, carboxyl, ester, sulfinyl, sulfonyl, alkylthio, or phenylthio. If possible, the above-mentioned substituents may be further substituents, and it is also preferred that the above-mentioned alkyl group has a halogen atom as a substituent and becomes a trifluoromethyl or other haloalkyl group. The aforementioned substituents are preferably formed by any combination to create acid-degradable groups. Furthermore, the term "acid-decomposable group" refers to a group that decomposes to produce a polar group through the action of an acid, preferably a group that is released by the action of an acid to protect the structure of the polar group. The aforementioned polar group and release group are as described above.

[0331] Next, the cation (ZaI-2) will be explained. In the cation (ZaI-2) system formula (ZaI), R 201 to R 203 independently represent cations with organic groups that do not possess aromatic rings. An aromatic ring also includes aromatic rings containing heteroatoms. The number of carbon atoms in the non-aromatic organic groups of R 201 to R 203 is preferably 1 to 30, more preferably 1 to 20. R 201 to R 203 are each independently, preferably alkyl, cycloalkyl, allyl or vinyl, more preferably linear or branched 2-oxoalkyl, 2-oxocycloalkyl or alkoxycarbonylmethyl, and even more preferably linear or branched 2-oxoalkyl.

[0332] Alkyl and cycloalkyl groups of R 201 to R 203, for example, include straight-chain alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl). R 201 to R 203 can be further substituted with halogen atoms, alkoxy groups (e.g., carbon 1 to 5), hydroxyl groups, cyano groups, or nitro groups. The substituents of R 201 to R 203 are respectively independent, or preferably formed by any combination of substituents to form acid-degradable groups.

[0333] Next, the cation (ZaI-3b) will be explained. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0334] [Chemical Formula 70]

[0335] In formula (ZaI-3b), R1c to R5c independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atoms, hydroxyl, nitro, alkylthio or arylthio. R6c and R7c independently represent a hydrogen atom, an alkyl group (e.g., tert-butyl), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. Rx and Ry independently represent alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl, or vinyl, respectively. The substituents R1c to R7c, as well as Rx and Ry, are respectively, independently, and preferably formed by any combination of substituents, into acid-degradable groups.

[0336] Any two or more of R1c to R5c, R5c and R6c, R6c and R7c, R5c and Rx, and Rx and Ry can be bonded to each other to form a ring, which can independently contain oxygen atoms, sulfur atoms, ketone groups, ester bonds or amide bonds. Examples of the aforementioned rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings composed of two or more such rings. Examples of rings include 3 to 10-membered rings, preferably 4 to 8-membered rings, and more preferably 5 or 6-membered rings.

[0337] Examples of alkyl groups formed by the bonding of any two or more of R1c to R5c, R6c and R7c, and Rx and Ry include alkyl groups such as butylyl and pentylyl. The methylene group in the alkyl group may be replaced by heteroatoms such as oxygen atoms. The group formed by the bond between R5c and R6c, and between R5c and Rx, is preferably a single bond or an alkyl group. Examples of alkyl groups include methylene and ethyl groups.

[0338] Rings formed by the mutual bonding of R1c to R5c, R6c, R7c, Rx, Ry, and any two or more of R1c to R5c, R5c and R6c, R6c and R7c, R5c and Rx, and Rx and Ry may have substituents.

[0339] Next, the cation (ZaI-4b) will be explained. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0340] [Chemical Formula 71]

[0341] In equation (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8. R 13 represents a hydrogen atom, a halogen atom (e.g., fluorine and iodine atoms), a hydroxyl group, an alkyl group, a haloalkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be the cycloalkyl group itself or a group that partially contains a cycloalkyl group). These groups may have substituents. R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, a haloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which can be the cycloalkyl group itself or a group that partially contains a cycloalkyl group). These groups may have substituents. When there are multiple R 14 groups, each of the above-mentioned groups, such as the hydroxyl group, represents an independent group. R 15 can independently represent alkyl, cycloalkyl, or naphthyl groups. Two R 15 groups can bond together to form a ring. When two R 15 groups bond together to form a ring, the ring skeleton can contain heteroatoms such as oxygen or nitrogen atoms. In one state, it is preferred that the two R 15s are alkyl groups and are bonded together to form a ring structure. Furthermore, the aforementioned alkyl group, the aforementioned cycloalkyl group, the aforementioned naphthyl group, and the ring formed by the bonded two R 15s may have substituents.

[0342] In formula (ZaI-4b), the alkyl groups of R13, R14, and R15 can be straight-chain or branched. The alkyl groups preferably have 1 to 10 carbon atoms. The alkyl groups are preferably methyl, ethyl, n-butyl, or tributyl, etc. Each substituent of R13~R15, as well as Rx and Ry, is preferably formed independently, or more preferably, by any combination of substituents to form an acid-decomposing group.

[0343] Next, we will explain equation (ZaII). In formula (ZaII), R 204 and R 205 independently represent aryl, alkyl, or cycloalkyl groups, respectively. The aryl group in R 204 and R 205 is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group in R 204 and R 205 can be a heterocyclic aryl group having an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocyclic aryl groups include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. As for the alkyl and cycloalkyl groups of R 204 and R 205, they are preferably straight-chain alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl or pentyl), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl or norbornyl).

[0344] The aryl, alkyl, and cycloalkyl groups in R 204 and R 205 can each independently have substituents. Examples of substituents that can be present in the aryl, alkyl, and cycloalkyl groups of R 204 and R 205 include alkyl groups (e.g., 1-15 carbon atoms), cycloalkyl groups (e.g., 3-15 carbon atoms), aryl groups (e.g., 6-15 carbon atoms), alkoxy groups (e.g., 1-15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. Furthermore, the substituents in R 204 and R 205 are preferably formed by any combination of substituents to create acid-degradable groups.

[0345] The following are specific examples of organic cations, but the invention is not limited thereto.

[0346] [Chemical Formula 72]

[0347] [Chemical Formula 73]

[0348] In compounds denoted by "M +X -", X - represents an anion. The description, specific examples, and preferred ranges of anions are the same as those described above regarding anions represented by X- in compound (N).

[0349] The photoacid generator (B) is preferably selected from at least one of the group consisting of compound (I) and compound (II).

[0350] (Compound (I)) Compound (I) is a compound having one or more structural sites X and one or more structural sites Y, and is a compound that produces an acid by irradiation with photochemical rays or radiation, comprising the first acidic site derived from structural site X and the second acidic site derived from structural site Y. Structural site X: Composed of anionic site A1- and cationic site M1+, and formed by irradiation with photochemical rays or radiation, forming the first acidic site represented by HA1. Structural site Y: Composed of anionic site A2- and cationic site M2+, and formed by irradiation with photochemical rays or radiation, resulting in a second acidic site represented by HA2. The above compound (I) satisfies the following condition I.

[0351] Condition I: In the above compound (I), the compound PI obtained by replacing the above-mentioned cation M1+ in the above-mentioned structural site X and the above-mentioned cation M2+ in the above-mentioned structural site Y with H+ has an acid dissociation constant a1 derived from the acidic site represented by HA1 obtained by replacing the above-mentioned cation M1+ in the above-mentioned structural site X with H+ and an acid dissociation constant a2 derived from the acidic site represented by HA2 obtained by replacing the above-mentioned cation M2+ in the above-mentioned structural site Y with H+, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0352] The cation sites M1+ and M2+ in compound (I) are structural sites containing positively charged atoms or groups of atoms, preferably organic cations with a monovalent charge, such as the organic cations represented by M+ mentioned above. The description, specific examples and preferred range of the portion other than the cation sites M1+ and M2+ in compound (I) are the same as those described above regarding the portion other than the cation sites M1+ and M2+ in compound (NI).

[0353] (Compound (II)) Compound (II) is a compound having two or more of the above-described structural sites X and one or more of the above-described structural sites Z, and is a compound that produces an acid comprising two or more first acidic sites derived from the above-described structural sites X and the above-described structural sites Z by irradiation with photochemical rays or radiation. Structural site Z: The site that can neutralize the nonionic nature of acids.

[0354] In compound (II), the definitions of structural site X, A1- and M1+ are synonymous with those in compound (I) above, and are also the same in preferred form. The description, specific examples and preferred range of structural site Z in compound (II) are the same as those described above for structural site Z in compound (NII). The description, specific examples, and preferred scope of the portion of compound (II) other than the cation site M1+ are the same as those described above for the portion of compound (NII) other than the cation site M1+.

[0355] Specific examples of sites other than cations that compounds (I) and (II) may have are the same as those of sites other than cations that compounds (NI) and (NII) may have described above.

[0356] The following are specific examples of photoacid generators (B), but are not limited to them.

[0357] [Chemical Formula 74]

[0358] [Chemical Formula 75]

[0359] [Chemical Formula 76]

[0360] [Chemical Formula 77]

[0361] When the composition of the present invention contains a photoacid generator (B), its content is not particularly limited, but it is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, relative to the total solid content of the composition of the present invention. The above-mentioned content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the composition of the present invention.

[0362] Photoacid generator (B) can be used alone or in combination with two or more.

[0363] <Acid Diffusion Control Agent (C)> The composition of this invention may contain an acid diffusion control agent (C) that is different from the compound (N). The acid diffusion control agent (C) acts as a quencher, which captures the acid generated from photoacid generators and the like during exposure and inhibits the reaction of acid-decomposing resin in the unexposed part caused by excess generated acid. There are no particular limitations on the types of acid diffusion control agents (C). For example, basic compounds (CA), low molecular weight compounds (CB) with nitrogen atoms and groups that can be removed by the action of acid, and compounds (CC) whose acid diffusion control ability is reduced or disappears by irradiation with photochemical rays or radiation. Examples of compounds (CC) include onium salt compounds (CD) that are relatively weak acids relative to photoacid generators (compound (N) or photoacid generator (B)), and basic compounds (CE) whose basicity is reduced or eliminated by exposure to photochemical rays or radiation. As a specific example of a basic compound (CA), for example, those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; as a specific example of a basic compound (CE) whose basicity is reduced or eliminated by irradiation with photochemical rays or radiation, those described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824 and paragraph

[0164] of International Publication No. 2020 / 066824; as a specific example of a low molecular weight compound (CB) having a nitrogen atom and a group that is removed by the action of an acid, those described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824. As a specific example of an onium salt compound (CD) that is a relatively weak acid relative to a photoacid generator, one can cite, for example, the one described in paragraphs

[0305] to

[0314] of International Publication No. 2020 / 158337.

[0364] In addition to the above, for example, well-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 may be used as acid diffusion control agents.

[0365] When the composition of the present invention contains an acid diffusion control agent (C), the content of the acid diffusion control agent (C) (or the sum of any plurality of such agents) is preferably 0.1 to 15.0% by mass relative to the total solid content of the composition of the present invention, and more preferably 1.0 to 15.0% by mass. In the composition of this invention, the acid diffusion control agent (C) can be used alone or in combination with two or more.

[0366] <Hydrophobic Resin (D)> The composition of the present invention may further contain a hydrophobic resin different from resin (A). Hydrophobic resins are preferably designed to exist on the surface of photoresist films. However, unlike surfactants, their molecules do not necessarily have hydrophilic groups and can also help to uniformly mix polar and non-polar substances. As an effect of adding hydrophobic resin, it can be cited that it controls the static and dynamic contact angle of the photoresist film surface with respect to water, and suppresses gas escape.

[0367] From the viewpoint of surface-biased membrane formation, the hydrophobic resin preferably has one or more of the following structures: fluorine atoms, silicon atoms, and CH3 moieties contained in the side chain portion of the resin; more preferably, it has two or more of these. The aforementioned hydrophobic resin preferably has a hydrocarbon group having five or more carbon atoms. These groups can exist in the main chain of the resin or can be substituted in the side chain. As a hydrophobic resin, the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306 can be cited as examples.

[0368] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin relative to the total solid content of the composition of the present invention is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 15.0% by mass.

[0369] <Surfactant (E)> The composition of this invention may contain surfactants. When surfactants are present, patterns with better adhesion and fewer development defects can be formed. Fluorine-based and / or silicone-based surfactants are preferred. As fluorine-based and / or silicon-based surfactants, examples include the surfactants disclosed in paragraphs

[0218] and

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

[0370] These surfactants can be used alone or in combination with more than one type.

[0371] When the composition of the present invention contains a surfactant, the content of the surfactant, relative to the total solid content of the composition of the present invention, is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0372] <Solvent(F)> The composition of the present invention preferably contains a solvent. The solvent preferably comprises at least one of (M1) and (M2), wherein (M1) is a propylene glycol monoalkyl ether carboxylic acid ester, and (M2) is at least one selected from the group consisting of propylene glycol monoalkyl ethers, lactates, acetates, alkoxypropionates, chain ketones, cyclic ketones, lactones, and alkyl carbonates. Furthermore, the solvent may further comprise components other than (M1) and (M2).

[0373] From the viewpoint of improving the coatability of the composition of the present invention and reducing the number of development defects in the pattern, it is preferable to combine the above-mentioned solvent and the above-mentioned resin. Since the above-mentioned resin has a good balance of solubility, boiling point and viscosity, the above-mentioned solvent can suppress uneven film thickness of the photoresist film and the generation of precipitates during spin coating. Details of the ingredients (M1) and (M2) are described in paragraphs

[0218] to

[0226] of International Publication No. 2020 / 004306, which are incorporated herein by reference.

[0374] When 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 amount of solvent.

[0375] The solvent content in the composition of the present invention is preferably set such that the solid component concentration is 0.1-30% by mass, more preferably 0.5-14.0% by mass. This further improves the coatability of the composition of the present invention. Furthermore, it enables the production of photoresist films with film thicknesses suitable for ArF immersion exposure and EUV exposure, which can be used to form high-precision micropatterns.

[0376] <Other Additives> The composition of the present invention may further contain a solubility-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility relative to the developer (e.g., a phenolic compound with a molecular weight of less than 1000, or an alicyclic or aliphatic compound containing a carboxyl group).

[0377] The aforementioned "dissolution-inhibiting compounds" refer to compounds with a molecular weight of less than 3000 that have reduced solubility in organic developing solutions due to acid decomposition.

[0378] The composition of this invention is suitable for use as a photosensitive composition for EUV exposure. EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm). Therefore, the number of incident photons is lower when exposed at the same sensitivity. Consequently, "photon shot noise," which has a probabilistic bias in the number of photons, has a greater impact, leading to LER degradation and bridging defects. To reduce photon shot noise, one method is to increase the exposure to increase the number of incident photons, but this must be balanced with the requirement for high sensitivity.

[0379] When the value of A, calculated by the following formula (1), is high, the absorption efficiency of EUV light and electron beam of the photoresist film formed by the photoresist composition is higher, which can effectively reduce photon shot noise. The value of A represents the absorption efficiency of EUV light and electron beam of the photoresist film by mass ratio. 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) The A value is preferably above 0.120. There is no particular upper limit, but when the A value is too large, the transmittance of EUV light and electron beam in the photoresist film will decrease, the optical image contour in the photoresist film will deteriorate, and it will be difficult to obtain a good pattern shape. Therefore, it is preferably below 0.240, and more preferably below 0.220.

[0380] Furthermore, in formula (1), [H] represents the molar ratio of hydrogen atoms in the total solid component of the composition of the present invention to all atoms in the total solid component, [C] represents the molar ratio of carbon atoms in the total solid component of the composition of the present invention to all atoms in the total solid component, [N] represents the molar ratio of nitrogen atoms in the total solid component of the composition of the present invention to all atoms in the total solid component, [O] represents the molar ratio of oxygen atoms in the total solid component of the composition of the present invention to all atoms in the total solid component, [F] represents the molar ratio of fluorine atoms in the total solid component of the composition of the present invention to all atoms in the total solid component, [S] represents the molar ratio of sulfur atoms in the total solid component of the composition of the present invention to all atoms in the total solid component, and [I] represents the molar ratio of iodine atoms in the total solid component of the composition of the present invention to all atoms in the total solid component. For example, when the composition of the present invention contains compound (N), resin (A), photoacid generator (B), acid diffusion control agent (C), and solvent, compound (N), resin (A), photoacid generator (B), and acid diffusion control agent (C) are equivalent to solid components. That is, all atoms of the total solid component are equivalent to the sum of all atoms derived from compound (N), all atoms derived from resin (A), all atoms derived from photoacid generator (B), and all atoms derived from acid diffusion control agent (C). For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid component to all atoms of the total solid component. Based on the above example, [H] represents the molar ratio of the sum of hydrogen atoms derived from compound (N), hydrogen atoms derived from resin (A), hydrogen atoms derived from photoacid generator (B), and hydrogen atoms derived from acid diffusion control agent (C) to the sum of all atoms derived from compound (N), all atoms derived from resin (A), all atoms derived from photoacid generator (B), and all atoms derived from acid diffusion control agent (C).

[0381] The A value can be calculated by calculating the atomic ratio when the structure and content of the constituent components of the total solid components in the composition of the present invention are known. Furthermore, even when the constituent components are unknown, the atomic ratio can be calculated using analytical methods such as elemental analysis for the photoresist film obtained by evaporating the solvent components of the composition of the present invention.

[0382] <Photoresist film and pattern formation methods> There is no particular limitation on the order of the pattern forming method using the composition of the present invention, but it is preferred to include the following processes. Process 1: A process of forming a photoresist film on a substrate using the components of the present invention. Process 2: The process of exposing the photoresist film. Process 3: The process of developing the exposed photoresist film using a developing solution. The steps of each of the above processes will be described in detail below.

[0383] (Process 1: Photoresist film formation process) Process 1 is a process of forming a photoresist film on a substrate using the components of this invention. The components of this invention are as described above.

[0384] As a method for forming a photoresist film on a substrate using the components of the present invention, for example, a method of coating the components of the present invention onto a substrate can be cited. Furthermore, it is preferable to filter the components of the present invention with a filter as needed before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. As a filter, filters with different pore sizes and / or materials can be combined. For example, a filtration process can be performed by first using a polyethylene filter with a pore size of 50 nm, then using a nylon filter with a pore size of 10 nm, and finally using a polyethylene filter with a pore size of 5 nm.

[0385] The components of this invention can be applied to a substrate (e.g., a silicon or silicon dioxide coating) for manufacturing integrated circuit elements using a suitable coating method such as a spin coater or a coating machine. Spin coating using a spin coater is preferred. The rotation speed when using a spin coater is preferably 1000-3000 rpm. After coating the components of this invention, the substrate can be dried to form a photoresist film. Furthermore, various substrate films (inorganic films, organic films, anti-reflective films) can be formed on the underside of the photoresist film, as needed.

[0386] As a drying method, for example, drying by heating can be cited. Heating can be carried out using the equipment provided in a conventional exposure machine and / or developing machine, or it can be carried out using a hot plate. The heating temperature is preferably 80~150°C, more preferably 80~140°C, and even more preferably 80~130°C. The heating time is preferably 30~1000 seconds, more preferably 60~800 seconds, and even more preferably 60~600 seconds.

[0387] There is no particular limitation on the thickness of the photoresist film, but from the viewpoint of forming finer patterns with higher precision, a thickness of 10 to 120 nm is preferred. Specifically, when using EUV exposure, the thickness of the photoresist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When using ArF immersion exposure, the thickness of the photoresist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0388] In addition, a topcoat composition can be used to form a topcoat on the top layer of the photoresist film. The composition of the top coating is preferably not mixed with the photoresist film and can be uniformly coated on the upper layer of the photoresist film. The top coating is not particularly limited and can be formed by previously known methods, for example, the top coating can be formed according to paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543. For example, it is preferable to form a top coating containing an alkaline compound, such as that described in Japanese Patent Application Publication No. 2013-61648, on the photoresist film. Specific examples of alkaline compounds that can be contained in the top coating include alkaline compounds that can be contained in photosensitive or radiosensitive linear resin compositions. The top coating is preferably a compound containing at least one group or bond selected from the group consisting of ether, thioether, hydroxyl, thiol, carbonyl and ester bonds.

[0389] (Process 2: Exposure Process) Process 2 is a process for exposing the photoresist film. One method of exposure is to irradiate the formed photoresist film with photochemical rays or radiation through a prescribed mask. Examples of photochemical rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Far ultraviolet light with wavelengths below 250 nm, more preferably below 220 nm, and especially preferably 1-200 nm can be cited. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams. The preferred process for exposing the photoresist film is EUV exposure.

[0390] It is preferable to bake (heat) after exposure and before development. Baking promotes the reaction of the exposed part, thereby improving sensitivity and pattern shape. The preferred heating temperature is 80~150℃, more preferably 80~140℃, and even more preferably 80~130℃. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be carried out using the equipment found in conventional exposure machines and / or developing machines, or it can be done using hot plates, etc. This process is also known as post-exposure baking.

[0391] (Process 3: Development Process) Process 3 uses a developer to develop the exposed photoresist film to form a pattern. The developer can be an alkaline developer or a developer containing organic solvents (hereinafter also referred to as an organic developer).

[0392] Examples of development methods include, for instance, immersing the substrate in a tank filled with developer for a certain time (immersion method), using surface tension to cause developer to accumulate on the substrate surface and leave it to stand for a certain time to perform development (puddle method), spraying developer onto the substrate surface (spraying method), and continuously spraying developer from a nozzle on a substrate rotating at a certain speed while scanning at a certain speed (dynamic distribution method). Furthermore, after the developing process, a process can also be implemented where the developing process is stopped while the solvent is being replaced with another solvent. The development time is only the time required for the resin in the unexposed areas to fully dissolve, and there are no particular restrictions. It is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds. The optimal temperature for the developer is 0~50℃, and more preferably 15~35℃.

[0393] Alkaline developer is preferably an alkaline aqueous solution containing an alkali. There are no particular limitations on the type of alkaline aqueous solution; examples include alkaline aqueous solutions containing quaternary ammonium salts (represented by tetramethylammonium hydroxide), inorganic bases, primary amines, secondary amines, tertiary amines, alkanolamines, or cyclic amines. Among these, an aqueous solution of a quaternary ammonium salt (represented by tetramethylammonium hydroxide, TMAH) is preferred. Appropriate amounts of alcohols, surfactants, etc., can be added to the alkaline developer. The alkali concentration of the alkaline developer is typically preferred to be 0.1% to 20% by mass. The pH of the alkaline developer is typically preferred to be 10.0 to 15.0.

[0394] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0395] The solvents described above can be mixed in multiple ways, or mixed with solvents other than those described above, or with water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and most preferably substantially water-free. The content of organic solvent relative to the organic developer, relative to the total amount of developer, is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and especially preferably 95% by mass or more and 100% by mass or less.

[0396] (Other processes) The above-mentioned pattern formation method preferably includes a cleaning process with rinsing solution after process 3.

[0397] As a rinsing solution used in the rinsing process following development with an alkaline developer, pure water can be cited as an example. Furthermore, an appropriate amount of surfactant can be added to the pure water. An appropriate amount of surfactant can also be added to the rinsing solution.

[0398] The rinsing solution used in the rinsing process after the developing process using an organic developer is not particularly restricted, as long as it does not dissolve the pattern. Solutions containing common organic solvents can be used. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0399] There are no particular limitations on the rinsing process. For example, methods such as continuously spraying rinsing liquid onto a substrate rotating at a certain speed (spin coating), immersing the substrate in a tank filled with rinsing liquid for a certain period of time (immersion), and spraying rinsing liquid onto the surface of the substrate (spraying). Furthermore, the pattern forming method can include a post-bake process after the washing process. This process removes residual developer and washing solution between and inside the pattern through baking. Additionally, this process also anneals the photoresist pattern and improves its surface roughness. The post-wash heating process is typically performed at 40–250°C (preferably 90–200°C) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0400] Furthermore, the formed pattern can be used as a mask to perform etching on the substrate. That is, the pattern formed in process 3 can be used as a mask to process the substrate (or the lower film and substrate) and form a pattern on the substrate. There are no particular limitations on the processing method of the substrate (or the lower film and the substrate), but it is preferable to use the pattern formed in process 3 as a mask and form the pattern on the substrate (or the lower film and the substrate) by dry etching. Dry etching is preferably oxygen plasma etching.

[0401] The components of this invention and the various materials used in the pattern forming method of this invention (e.g., solvents, developers, rinsing solutions, components for forming antireflective films, components for forming topcoats, etc.) are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, further preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. There is no particular limitation on the lower limit, but it is preferably 0 ppt or more. Examples of metallic impurities include, for example, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0402] As a method for removing impurities such as metals from various materials, filtration using a filter can be cited as an example. Details of filtration using a filter are described in paragraph

[0321] of International Publication No. 2020 / 004306.

[0403] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as the raw materials for various materials, filtering the raw materials for various materials with filters, and using TEFLON (registered trademark) to form a lining in the apparatus to carry out distillation under conditions that suppress contamination as much as possible.

[0404] In addition to filtration, impurities can also be removed using adsorption materials, or a combination of filtration and adsorption materials can be used. Known adsorption materials can be used, such as inorganic adsorption materials like silica gel and zeolite, and organic adsorption materials like activated carbon. To reduce impurities such as metals contained in these materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the metal content in the cleaning solution used to clean the manufacturing apparatus. The metal content in the used cleaning solution is preferably less than 100 ppt by mass, more preferably less than 10 ppt by mass, and even more preferably less than 1 ppt by mass. There is no particular limitation on the lower limit, but it is preferably 0 ppt by mass or more.

[0405] Conductive compounds can be added to organic processing solutions such as rinsing solutions to prevent malfunctions in the solution piping and various components (filters, O-rings, and tubing) caused by static electricity and subsequent electrostatic discharge. There are no particular limitations on the conductive compounds; methanol is an example. The amount added is not particularly limited, but from the viewpoint of maintaining better developing or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. There are no particular limitations on the lower limit, but it is preferably 0.01% by mass or more. For example, SUS (stainless steel) or various pipes coated with anti-static treatments such as polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can be used for chemical fluid piping. Similarly, for filters and O-rings, anti-static treatments such as polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can also be used.

[0406] Manufacturing Methods of Electronic Devices The present invention also relates to a method for manufacturing an electronic device including the above-described pattern forming method, and an electronic device manufactured by the method. As a preferred embodiment of the electronic device described in this specification, it may be embodied in electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.). [Example]

[0407] The present invention will be described in more detail below based on embodiments. The materials, amounts, ratios, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0408] The compounds used in the examples and comparative examples are described below.

[0409] <Compound (N)> As compounds (N), X-1 to X-27 were used. The proportion of repeating units in X-25 is the mass ratio (mass%) of each repeating unit contained in X-25 relative to all repeating units. The weight-average molecular weight (Mw) of X-25 is 10100, and the dispersity (Mw / Mn) is 1.61. Furthermore, Z-1 to Z-7 were used in the comparative examples. Although Z-1 to Z-7 are not compounds (N), they are listed in the compound (N) column for convenience.

[0410] [Chemical Formula 78]

[0411] [Chemical Formula 79]

[0412] [Chemical Formula 80]

[0413] [Chemical Formula 81]

[0414] [Chemical Formula 82]

[0415] (Synthesis Example 1: Synthesis of X-1) The synthesis example of X-1 is shown below.

[0416] [Chemical Formula 83]

[0417] Magnesium (8.9 g) was added to tetrahydrofuran (THF) (390 mL) to obtain a mixture. 4-Bromo-2-fluorotrifluorotoluene (94.0 g) was added dropwise to the obtained mixture. The mixture was then stirred for 1 hour to prepare Grignard reagent X-1-1. Grignard reagent X-1-1 was cooled to 0 °C and thionyl chloride (23.0 g) was added dropwise. After stirring the mixture for 1 hour, 1 mol / L hydrochloric acid (300 mL) was added to the mixture while maintaining the temperature at 0 °C. The reaction product formed in the mixture was extracted with ethyl acetate (300 mL). The obtained organic phase was washed three times with water (300 mL), and the solvent was distilled off from the organic phase. X-1-A (25.3 g) (35% yield) was obtained by crystallization of the concentrate with heptane (100 mL).

[0418] [Chemical Formula 84]

[0419] Magnesium (5.0 g) was added to tetrahydrofuran (200 mL) to obtain a mixture. 4-Bromo-2-fluorotrifluorotoluene (48.5 g) was added dropwise to the obtained mixture. The mixture was then stirred for 1 hour to prepare Grignard reagent X-1-2. Grignard reagent X-1-2 was cooled to -10°C, and X-1-A (25.0 g) was added. Subsequently, trimethylsilyl trifluoromethanesulfonate (TMSOTf) (103.6 g) was added dropwise to the mixture. After stirring the mixture for 1 hour, water (200 mL) was added dropwise to the mixture. The reaction product generated in the mixture was extracted with dichloromethane (200 mL). The obtained organic phase was washed three times with water (200 mL), and then the solvent was distilled off the organic phase. X-1-B (9.3 g) (yield 21%) was obtained by crystallizing the obtained concentrate with diisopropyl ether (100 mL).

[0420] [Chemical Formula 85]

[0421] Dichloromethane (100 mL) and water (100 mL) were mixed, and X-1-3 (4.0 g) and X-1-B (6.7 g) were added. After stirring for 1 hour, the aqueous layer was removed, and the organic layer was washed with 0.1 mol / L hydrochloric acid (100 mL) and water (100 mL). The solvent was distilled off, thus yielding X-1 (7.9 g) (95% yield).

[0422] Other compounds (N) were synthesized in the same manner as X-1.

[0423] <Resin (A)> As resin (A), A-1 to A-27 were used. Table 1 shows the content (moles%), weight average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit contained in each resin. The content of repeating units is the ratio (molar ratio) of each repeating unit contained in each resin to all repeating units. In Table 1, the content of repeating units in each resin corresponds to the order of repeating units in the structural formula of each resin shown below. For example, in A-1, the content of repeating units on the left is 25 mol%, the content of repeating units in the center is 30 mol%, and the content of repeating units on the right is 45 mol%. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin were determined by GPC (carrier: tetrahydrofuran (THF)) (converted from polystyrene). Furthermore, the content of repeating units was determined by 13C-NMR (nuclear magnetic resonance).

[0424] [Chemical Formula 86]

[0425] [Chemical Formula 87]

[0426] [Chemical Formula 88]

[0427] [Table 1]

[0428] <Photoacid Generator (B)> B-1 to B-11 were used as photoacid generators (B).

[0429] [Chemical Formula 89]

[0430] [Chemical Formula 90]

[0431] <Acid diffusion control agent> C-1 to C-7 were used as acid diffusion control agents.

[0432] [Chemical Formula 91]

[0433] <Hydrophobic resin> As hydrophobic resins, D-1 to D-6 as shown in Table 2 below were used. Table 2 shows the types and contents (moles%), weight average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit contained in each resin. The content of repeating units is the ratio (moles ratio) of each repeating unit contained in each resin to all repeating units. The types of each repeating unit are shown by the structure of the corresponding monomer. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin were determined by GPC (carrier: tetrahydrofuran (THF)) (converted from polystyrene). Furthermore, the content of repeating units was determined by 13C-NMR (nuclear magnetic resonance).

[0434] [Table 2]

[0435] The structures of monomers ME-1 to ME-13 corresponding to each repeating unit constituting the hydrophobic resin shown in Table 2 are as follows.

[0436] [Chemical Formula 92]

[0437] <surfactants> E-1 to E-3 were used as surfactants. E-1: MEGAFAC F176 (DIC (stock) manufacturing, fluorinated surfactant). E-2: MEGAFAC R08 (DIC (stock) manufacturing, fluorine and silicon-based surfactant). E-3: PF656 (manufactured by OMNOVA, a fluorinated surfactant)

[0438] Solvent F-1 to F-9 were used as solvents. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6:2-Heptanone F-7: Ethyl lactate F-8: γ-Butyrolactone F-9: Propylene carbonate

[0439] [Preparation of photoresist composition] The components shown in Tables 3 and 4 below were mixed to achieve a solid component concentration of 2% by mass. The resulting mixture was then filtered in the following order: first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm, thereby preparing the photoresist compositions (Re-1 to Re-42). In the photoresist compositions, the term "solid component" refers to all components other than the solvent. In Tables 3 and 4, the contents (mass %) of compound (N), resin (A), photoacid generator (B), acid diffusion control agent, hydrophobic resin, and surfactant refer to the percentage of content relative to the total solid content of the photoresist composition. The solvent mixing ratio refers to the proportion (mass ratio) of each solvent when all solvents are set to 100. When two or more components are used, each type and its content are separated by " / ". For example, "X-17 / X-18 / X-24" in the photoresist composition Re-28 indicates that three compounds (N) X-17, X-18, and X-24 are used, and "20.0 / 3.2 / 22.6" indicates that the content of X-17 is 20.0% by mass, the content of X-18 is 3.2% by mass, and the content of X-24 is 22.6% by mass. The obtained photoresist composition was used in the embodiments and comparative examples.

[0440] [Table 3]

[0441] [Table 4]

[0442] [Pattern formation (1): EUV exposure, alkaline development] The lower layer film forming composition AL412 (manufactured by Brewer Science) was coated onto a silicon wafer and baked at 205°C for 60 seconds to form a lower layer film with a thickness of 20 nm. The photoresist composition shown in Table 5 was coated onto the lower layer film and baked at 100°C for 60 seconds to form a photoresist film with a thickness of 30 nm. The silicon wafer with the obtained photoresist film was patterned using an EUV exposure apparatus (Exitech Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma (σ) 0.68, inner sigma (σ) 0.36). A mask with a line size of 16 nm and a line-to-space ratio of 1:1 was used as a reticle. The exposed photoresist film was baked at 90°C for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. After that, it was rotated to dry to obtain a positive pattern.

[0443] [Pattern Formation (2): EUV Exposure, Organic Solvent Development] The lower layer film composition AL412 (manufactured by Brewer Science) was coated onto a silicon wafer and baked at 205°C for 60 seconds to form a lower layer film with a thickness of 20 nm. The photoresist composition shown in Table 6 was coated onto the lower layer film and baked at 100°C for 60 seconds to form a photoresist film with a thickness of 30 nm. An EUV exposure apparatus (Exitech Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma (σ) 0.68, inner sigma (σ) 0.36) was used to pattern a silicon wafer with the obtained photoresist film. As a marker, a mask with a line size of 16 nm and a line-to-space ratio of 1:1 was used. After the exposed photoresist film was baked at 90°C for 60 seconds, it was developed with n-butyl acetate for 30 seconds and then rotated to dry to obtain a negative pattern.

[0444] [LWR Performance Evaluation] Using a length-measuring scanning electron microscope (CD-SEM, Hitachi, Ltd. S-9380II), a 16nm (1:1) line and spatial pattern, resolved with the optimal exposure at a line pattern with an average linewidth of 16nm, was observed from above. The linewidth of the pattern was observed at any point (100), and its standard deviation (σ) was calculated. The measurement deviation of the linewidth was evaluated using 3σ (nm), and denoted as LWR (nm). A smaller LWR value indicates better LWR performance. The preferred LWR (nm) is 4.3nm or less, more preferably 3.9nm or less, and even more preferably 3.5nm or less. The results are shown in Tables 5 and 6.

[0445] [Resolution Evaluation] Using the photoresist pattern formation method described above, the optimal exposure Eop (mJ / cm²) for forming line and spatial patterns of the target size was determined. The limiting resolution within this Eop was then determined using a length-measuring scanning electron microscope (CD-SEM, Hitachi, Ltd. S-9380II). Specifically, this is the minimum size of the pattern that can be resolved without collapse when the exposure is gradually increased from the optimal exposure Eop to form the line and spatial patterns. This is defined as the "limiting resolution (nm)". The smaller the limiting resolution value, the better the resolution. Furthermore, the limiting resolution (nm) is preferably below 14.0 nm, more preferably below 13.0 nm, and even more preferably below 12.0 nm. The results are shown in Tables 5 and 6.

[0446] [Table 5]

[0447] [Table 6]

[0448] As can be seen from the results in Tables 5 and 6, the photoresist composition of the embodiments exhibits excellent LWR performance and resolution when forming extremely fine patterns.

[0449] none

Claims

1. A photosensitive or radiosensitive linear resin composition comprising a compound (N) having an anion and a cation represented by the following general formula (N1) and a resin (A) whose polarity increases upon decomposition by acid action, [Chemical Formula 1] In the general formula (N1), RN1, RN2, and RN3 independently represent haloalkyl or halogen atoms, wherein, At least one of RN1, RN2, and RN3 represents a haloalkyl group, and at least one represents a halogen atom. k1 represents an integer from 2 to 5, and k2 and k3 independently represent integers from 1 to 5. A plurality of RN1s can be the same or different. Similarly, a plurality of RN2s can be the same or different. A plurality of RN3s can be the same or different. Wherein, if k1 represents 2, both RN1s are in the meta position; if k2 represents 2, both RN2s are in the meta position; and k3 represents 1, then RN3 is in the ortho position. If k1 represents 2, both RN1s are in the meta position; if k2 represents 2, both RN2s are in the meta position; and k3 represents 2, then the two RN3s are not simultaneously in the meta position. If k1 represents 2, both RN1s are in the meta position; if k2 represents 1, RN2 is in the para position; and k3 represents 1, then RN3 is in the ortho or meta position. If k1 represents 3, two RN1s are in the meta position and one RN1 is in the para position; if k2 represents 1, RN2 is in the para position; and if k3 represents 1, then RN3 is in the ortho or meta position. If k1 represents 2, both RN1s are in the ortho position; if k2 represents 2, both RN2s are in the ortho position; and if k3 represents 1, then RN3 is in the ortho position. RN4, RN5, and RN6 independently represent substituents, where RN4, RN5, and RN6 do not represent halogen atoms or haloalkyl groups. When there are multiple RN4s, they can be the same or different. When there are multiple RN5s, they can be the same or different. When there are multiple RN6s, they can be the same or different. k4 represents an integer from 0 to 3, and k5 and k6 independently represent integers from 0 to 4. At least two aromatic rings in the general formula (N1) can be bonded by single bonds or linker groups. The cation represented by the above general formula (N1) satisfies conditions 1 and 2 below, or satisfies condition 2 below: Condition 1: k1 represents an integer from 2 to 4, in the aromatic ring bonded by RN1, one meta position has RN1, and the other meta position does not have RN1; Condition 2: k2 and k3 each independently represent integers from 2 to 4, in the aromatic ring bonded by RN2, one meta position has RN2, and the other meta position does not have RN2, and in the aromatic ring bonded by RN3, one meta position has RN3, and the other meta position does not have RN3.

2. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, The cation represented by the above general formula (N1) is the cation represented by the following general formula (N2). [Chemical Formula 2] In general formula (N2), RN1, RN2, RN3, RN4, RN5, RN6, k2, k3, k4, k5 and k6 respectively represent the same meaning as RN1, RN2, RN3, RN4, RN5, RN6, k2, k3, k4, k5 and k6 in general formula (N1). At least two aromatic rings in general formula (N2) can be bonded by single bonds or linker groups.

3. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, The cation represented by the above general formula (N1) is the cation represented by the following general formula (N3), [Chemical Formula 3] In general formula (N3), RN1, RN2, RN3, RN4, RN5, RN6 and k4 have the same meaning as RN1, RN2, RN3, RN4, RN5, RN6 and k4 in general formula (N1), and k7 and k8 independently represent integers from 0 to 3. At least two aromatic rings in general formula (N3) can be linked by single bonds or linking groups.

4. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, The cation represented by the above general formula (N1) is the cation represented by the following general formula (N4) or (N5). [Chemical Formula 4] In general formulas (N4) and (N5), RN1, RN2, RN3, RN4, RN5, RN6 and k4 respectively represent the same meaning as RN1, RN2, RN3, RN4, RN5, RN6 and k4 in general formula (N1), and k7 and k8 respectively independently represent integers from 0 to 3. At least two aromatic rings in general formula (N4) can be linked by single bonds or linking groups, and at least two aromatic rings in general formula (N5) can be linked by single bonds or linking groups.

5. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, All halogen atoms represented by RN1, RN2 and RN3 are fluorine atoms.

6. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, All haloalkyl groups represented by RN1, RN2 and RN3 are fluoroalkyl groups.

7. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, At least one of the haloalkyl groups represented by RN1, RN2 and RN3 has 1 to 4 carbon atoms.

8. A photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 7, wherein, The anion is an organic anion having at least one of the group consisting of a group represented by the following general formula (N6), *-SO3- and *-CO2-, [Chemical Formula 5] LN1 and LN2 independently represent -SO2- or -CO-, and * indicates the bond position.

9. A photoresist film formed using a photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 8.

10. A pattern forming method comprising: a process of forming a photoresist film on a substrate using a photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 8; a process of exposing the photoresist film; and a process of developing the exposed photoresist film using a developing solution.

11. A method for manufacturing an electronic device, comprising the pattern forming method described in claim 10.