Photosensitive radioactive or radiosensitive linear resin compositions, photosensitive radioactive or radiosensitive linear films, patterning methods, manufacturing methods of electronic components, and compounds.

Abstract

The present invention provides a photosensitive or radiosensitive linear resin composition containing a compound (I) having an ionic structure and a zwitterionic structure that produces acid by irradiation with photochemical rays or radiation, a photosensitive or radiosensitive linear film using the above-mentioned photosensitive or radiosensitive linear resin composition, a pattern forming method, a method for manufacturing electronic components, and the compound.

Description

Technical Field

[0001] This invention relates to photosensitive radioactive or radioactive linear resin compositions, photosensitive radioactive or radioactive linear films, patterning methods, manufacturing methods of electronic components, and compounds. More specifically, this invention relates to ultra-microlithography processes applicable to manufacturing processes of LSI (Large Scale Integration) and high-capacity microchips, nanoimprint dies fabrication processes, and high-density information recording media, as well as photosensitive radioactive or radioactive linear resin compositions, photosensitive radioactive or radioactive linear films, patterning methods, manufacturing methods of electronic components, and compounds preferably applicable to other photosensitive etching processes. Prior Technology

[0002] Previously, in the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs, microfabrication was achieved using photoresist composition 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 trended towards shorter wavelengths, moving from gamma rays to i-rays, and further to KrF excimer lasers. 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 so-called immersion method is being developed, which involves filling the space between the projection lens and the sample with a high-refractive-index liquid (hereinafter referred to as "immersion liquid").

[0003] Furthermore, in addition to excimer laser light, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) light is currently 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] For example, Patent Documents 1 and 2 describe photosensitive or radiosensitive linear resin compositions containing compounds represented by a specific general formula (Z1) that produce acid upon irradiation by photosensitive rays or radiation.

[0005] Patent document 3 describes a compound represented by a specific formula (I), a resin that is insoluble or sparingly soluble in an alkaline aqueous solution but soluble in an alkaline aqueous solution by the action of an acid, and a photoresist composition containing an acid generating agent.

[0006] [Previous Technical Documents]

[0007] [Patent Document]

[0008] Patent Document 1: Japanese Patent Laid-Open No. 2013-167825

[0009] Patent Document 2: International Publication No. 2013 / 121819

[0010] Patent Document 3: Japanese Patent Laid-Open No. 2012-189977 Summary of the Invention Problems to be Solved by the Invention

[0011] In recent years, the miniaturization of patterns has been continuously developing, and further improvement in various properties of a photosensitive or radiation-sensitive resin composition used for forming such patterns has been required.

[0012] According to the prior art described in Patent Documents 1 to 3, although properties such as sensitivity are excellent, there is still room for further improvement, particularly in terms of the generation of residues in fine patterns.

[0013] Therefore, an object of the present invention is to provide a photosensitive or radiation-sensitive resin composition having excellent storage stability, and capable of obtaining an excellent pattern shape while greatly reducing the generation of residues when forming a fine pattern (particularly, a line width or a gap width of 50 nm or less). Another object of the present invention is to provide a photosensitive or radiation-sensitive film, a pattern forming method, a method for manufacturing an electronic component, and a compound using the above photosensitive or radiation-sensitive resin composition. Means for Solving the Problems

[0014] The present inventors have found that the above problems can be solved by the following constitution.

[0015] [1]

[0016] A photosensitive or radiation-sensitive resin composition containing a compound (I) having an ionic structure and an amphoteric ionic structure that generates an acid upon irradiation with actinic rays or radiation.

[0017] [2]

[0018] As described in [1], the photosensitive or radiosensitive linear resin composition, wherein the compound (I) is a compound in which one or more cationic groups and two or more anionic groups are covalently linked.

[0019] [3]

[0020] As described in [1] or [2], the photosensitive or radiosensitive linear resin composition, wherein the compound (I) is a compound in which one cationic group and two anionic groups are covalently linked.

[0021] [4]

[0022] The photosensitive or radiosensitive linear resin composition as described in any one of [1] to [3], wherein the above-mentioned ionic structure and the above-mentioned zwitterionic structure are each structures containing acid anionic groups, and the above-mentioned compound (I) generates a plurality of acid groups with different pKa by irradiation by photosensitive rays or radiation.

[0023] [5]

[0024] The photosensitive or radiosensitive linear resin composition as described in any one of [1] to [4], wherein the compound (I) is a compound represented by any one of the following general formulas (I)-1 to (I)-3.

[0025] [Chemical Formula 1]

[0026] In general formulas (I)-1 to (I)-3, A11- to A16- represent acidic anionic groups, C11+ to C16+ represent cationic groups, L11 to L14 represent divalent organic groups, and L15 represents trivalent organic groups.

[0027] [6]

[0028] As described in [5], in the photosensitive radioactive or radiosensitive linear resin composition, wherein in compound PI-1, which is formed by replacing the counter cation of the acid anionic group represented by A11- with H+ and adding H+ to the acid anionic group represented by A12-, the pKa of the group represented by A11H is lower than the pKa of the group represented by A12H, and in the compound represented by general formula (I)-2, the counter cation of the acid anionic group represented by A13- is... In compound PI-2, which is formed by replacing H+ with H+ and adding H+ to the acidic anionic group represented by A14-, the pKa of the group represented by A13H is lower than that of the group represented by A14H. In compound PI-3, which is formed by adding H+ to the acidic anionic group represented by A15- and replacing the counter cation of the acidic anionic group represented by A16- with H+, the pKa of the group represented by A15H is lower than that of the group represented by A16H.

[0029] [7]

[0030] As described in [5] or [6], in the above formulas (I)-1 to (I)-3, A11-, A13- to A16- respectively independently represent the acid anionic groups represented by the following formulas (A-1) or (A-2).

[0031]

[0032] In the above formulas (A-1) to (A-2), RA represents an organic group, and * represents a bond position.

[0033] [8]

[0034] The photosensitive or radiosensitive linear resin composition as described in any one of [5] to [7], wherein A12- in formula (I)-1 represents an acidic anionic group represented by any one of formulas (B-1) to (B-3).

[0035]

[0036] In the above equations (B-1) to (B-3), * indicates the bond position.

[0037] [9]

[0038] A photosensitive radioactive or radioactive linear membrane formed from a photosensitive radioactive or radioactive linear resin composition as described in any one of [1] to [8].

[0039]

[10]

[0040] A pattern forming method comprising the following processes: forming a photosensitive radioactive or radioactive linear resin composition on a substrate by means of any one of [1] to [8]; exposing the photosensitive radioactive or radioactive linear film; and developing the exposed photosensitive radioactive or radioactive linear film using a developing solution.

[0041]

[11]

[0042] A method for manufacturing an electronic component, comprising the pattern forming method as described in

[10] .

[0043]

[12]

[0044] A compound represented by any one of the following general formulas (IA)-1 to (IA)-3.

[0045]

[0046] In general formulas (IA)-1 to (IA)-3, A11- and A13- to A16- independently represent acid anionic groups represented by formulas (A-1) or (A-2) below, A12- represents acid anionic groups represented by any one of formulas (B-1) to (B-3) below, C11+ to C16+ independently represent cationic groups, L11 to L14 independently represent divalent organic groups, and L15 represents trivalent organic groups.

[0047] [Chemical Formula 5]

[0048] In the above formulas (A-1) to (A-2), RA represents an organic group, and * represents a bonding position.

[0049]

[0050] In the above formulas (B-1) to (B-3), * represents a bonding position. Effect of the Invention

[0051] According to the present invention, a photosensitive radiation-curable or radiation-sensitive resin composition with excellent storage stability can be provided. When forming a fine pattern (especially with a line width or gap width of 50 nm or less), an excellent pattern shape can be obtained while greatly reducing the generation of residues. Also, according to the present invention, a photosensitive radiation-curable or radiation-sensitive film, a pattern forming method, a method for manufacturing an electronic component, and a compound using the above photosensitive radiation-curable or radiation-sensitive resin composition can be provided. Embodiments

[0052] Hereinafter, the present invention will be described in detail.

[0053] The following description of the components of the present invention is sometimes based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0054] Regarding the description of the groups (atomic groups) in this specification, as long as it does not violate the gist of the present invention, those without the description of substitution and non-substitution include both groups without substituents and groups containing substituents. For example, the so-called "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). Also, in this specification, the so-called "organic group" refers to a group containing at least one carbon atom.

[0055] As a substituent, unless otherwise specified, a monovalent substituent is preferred.

[0056] In this specification, the so-called "actinic radiation" or "radiation" means, for example, far ultraviolet rays, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam) represented by the bright line spectrum of a mercury lamp and excimer lasers.

[0057] In this manual, the term "light" refers to photochemical rays or radiation.

[0058] In this specification, the term "exposure" unless otherwise specified includes not only exposure using bright-line spectra such as mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light, X-rays and EUV light, but also depiction using particle beams such as electron beams and ion beams.

[0059] In this manual, the term "~" is used to indicate that the values ​​recorded before and after it are included as lower and upper limits.

[0060] Unless otherwise specified, the bonding orientation of the divalent groups described in this specification is not limited. For example, in compounds represented by the formula "XYZ", when Y is -COO-, Y can be -CO-O- or -O-CO-. Furthermore, the above compounds can be either "X-CO-OZ" or "XO-CO-Z".

[0061] In this specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic acid means acrylic acid and methacrylic acid.

[0062] 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)).

[0063] 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.

[0064] All pKa values ​​described in this specification represent values ​​obtained by calculation using this software package.

[0065] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0066] Furthermore, pKa can also be determined using molecular orbital calculations. One specific method is to calculate it using the H+ dissociation free energy in aqueous solution based on thermodynamic cycles. Regarding the calculation of the H+ dissociation free energy, methods such as DFT (Density Functional Theory) can be used, but various other methods have been reported in the literature, and the calculation method is not limited to these. In addition, there are various software programs that can perform DFT, such as Gaussian16.

[0067] 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.

[0068] Furthermore, in this specification, pKa, as mentioned above, refers to "pKa in aqueous solution," but when the pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" is used.

[0069] The term "solid component" refers to components that form photosensitive or radiosensitive linear films and do not contain solvents. Furthermore, if a component forms a photosensitive or radiosensitive linear film, it is considered a solid component even if it is in liquid form.

[0070] Furthermore, 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, for example, be one, two, three, or more. Examples of substituents include monovalent nonmetallic groups other than hydrogen atoms, which may be selected from substituents T.

[0071] (Substituent T)

[0072] 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; and acetyl, benzoyl, isobutyl, propenyl, and methacrylamide. Alkyl groups such as methyl thiosulfate and methoxysulfate; alkyl thiosulfates such as methyl thiosulfate and tributyl thiosulfate; aryl thiosulfates such as phenyl thiosulfate and p-tolyl thiosulfate; alkyl; alkenyl; cycloalkyl; aryl; heteroaryl; hydroxyl; carboxyl; methyl sulfate; sulfonic acid; cyano; alkylamino carbonyl; arylamino carbonyl; sulfoamino; silyl; amino; monoalkylamino; dialkylamino; arylamino; and combinations thereof.

[0073] [Photosensitive or radiosensitive linear resin composition]

[0074] The photosensitive or radiosensitive linear resin composition involved in this invention (hereinafter also referred to as "the composition of this invention") is a photosensitive or radiosensitive linear resin composition containing a compound (I) having an ionic structure and a zwitterionic structure that produces acid by irradiation with photosensitive rays or radiation.

[0075] In this specification, the term "ionic structure" refers to the structure in which a pair of "positively charged functional groups (cationic groups)" and "negatively charged functional groups (anionic groups)" form an ion pair through ionic bonds (not through covalent bonds). To avoid confusion with "zwitterionic structure", it is also referred to as "free ionic structure" in this specification.

[0076] On the other hand, the so-called "zwitterionic structure" refers to a structure in which a pair of "positively charged functional groups (cationic groups)" and "negatively charged functional groups (anionic groups)" are linked by covalent bonds.

[0077] Furthermore, the term "via covalent bond" refers to both the state in which the aforementioned cationic group and the aforementioned anionic group are bonded by a single bond, and the state in which the aforementioned cationic group and the aforementioned anionic group are bonded by a linker group.

[0078] Because of the above-described structure, the present invention exhibits excellent preservation stability and can obtain excellent pattern shape while greatly reducing residue generation when forming fine patterns (especially with linewidth or gap width of 50 nm or less).

[0079] Although the reasons are still unclear, the following can be speculated.

[0080] As described below, the compound (I) included in the composition of the present invention can function as a compound for the acid required for the resin reaction of the exposed portion and as an acid diffusion control agent for capturing excess acid generated from the exposed portion. Furthermore, as mentioned above, because compound (I) has a zwitterionic structure with paired cationic and anionic groups covalently linked, compared to the case without a zwitterionic structure, the excessive movement of acid generated by compound (I) in the exposed portion of the film and compound (I) in the unexposed portion tends to be suppressed within the film (particularly between the exposed and unexposed portions). As a result, it is believed that by performing the desired reaction with high precision in the exposed portion, excellent pattern shapes can be obtained even when forming fine patterns (particularly with linewidths or gap widths of 50 nm or less).

[0081] Furthermore, as mentioned above, in addition to its zwitterionic structure, compound (I) also possesses a free ionic structure, which consists of paired cationic and anionic groups forming ion pairs via ionic bonds (not covalent bonds). Based on this composition, interactions between the cationic groups in the zwitterionic structure and the anionic groups in the free ionic structure, and vice versa, are readily observed in the composition. Therefore, it is assumed that the cationic groups, which are susceptible to nucleophilic attack, can exist stably in compound (I). Consequently, it is speculated that compound (I) is not easily decomposed during the storage of the composition, making the composition exhibit excellent storage stability.

[0082] Furthermore, compounds with zwitterionic structures have paired cationic and anionic groups linked by covalent bonds, which is why it is believed that the compounds will aggregate and easily produce residues when developed with alkaline developer (alkaline development) and organic solvent developer (organic solvent development). However, the compound (I) of the present invention has a free ionic structure in addition to a zwitterionic structure, which is believed to inhibit molecular aggregation and improve solubility in the above-mentioned alkaline developer and organic solvent developer, thereby greatly reducing the generation of residues.

[0083] The composition of this invention is preferably a photoresist composition, which can be a positive photoresist composition or a negative photoresist composition. Furthermore, it can be a photoresist composition for alkaline development or a photoresist composition for organic solvent development.

[0084] Furthermore, the composition of the present invention is preferably a chemically amplified photoresist composition, and more preferably a chemically amplified positive photoresist composition.

[0085] Photoresist composition, typically chemically amplified photoresist composition.

[0086] The various components of the present invention will now be described in detail.

[0087] <(I) Compounds with ionic and zwitterionic structures that produce acids through irradiation by photochemical rays or radiation>

[0088] As described above, the photosensitive or radiosensitive linear resin composition of the present invention contains a compound (I) (also referred to as "compound (I)") that has an ionic and zwitterionic structure and produces acid by irradiation with photosensitive rays or radiation.

[0089] As described above, the free ionic structure represents a structure in which paired cationic and anionic groups form ion pairs via ionic bonds (not covalent bonds), and more preferably, it represents a structure in which paired cationic and acidic anionic groups form ion pairs via ionic bonds.

[0090] As described above, the zwitterionic structure represents a structure in which paired cationic and anionic groups are linked by covalent bonds, preferably a structure in which paired cationic and acidic anionic groups are linked by covalent bonds.

[0091] In other words, both free ionic structures and zwitterionic structures are preferably structures containing acid anionic groups.

[0092] In compound (I), the terms "having a free ionic structure" and "having a zwitterionic structure" mean that it has a free ionic structure and a zwitterionic structure, respectively, and that the cationic and anionic groups in the free ionic structure are not the same as the cationic and anionic groups in the zwitterionic structure, respectively. That is, the cationic group in the free ionic structure will not also function as the cationic group in the zwitterionic structure, and the anionic group in the free ionic structure will not also function as the anionic group in the zwitterionic structure.

[0093] Therefore, in compound (I), in essence, at least one of the cationic and anionic groups in the free ionic structure is covalently linked to the zwitterionic structure.

[0094] Compound (I) may have one free ion structure or multiple free ion structures. When multiple free ion structures are present, they may be of the same type or different types.

[0095] Compound (I) may have one zwitterionic structure or multiple zwitterionic structures. When multiple zwitterionic structures are present, they may be of the same type or different types.

[0096] Compound (I) is a compound that produces acid by exposure to photochemical rays or radiation (photoacid generator).

[0097] The compound (I) is preferably formed by irradiation with photochemical rays or radiation, producing an acid group corresponding to the above-mentioned acid anionic group of the free ionic structure and an acid group corresponding to the above-mentioned acid anionic group of the zwitterionic structure.

[0098] In compound (I), the cationic group in the free ionic structure can be linked to the zwitterionic structure via a covalent bond, and the anionic group in the free ionic structure can be linked to the zwitterionic structure via a covalent bond.

[0099] As described above, the anionic group in the free ionic structure is preferably an acidic anionic group. Specifically, examples include organic groups containing an acidic anionic group represented by formula (A-1) or (A-2) described below, or organic groups containing an acidic anionic group represented by any one of formulas (B-1) to (B-3) described below.

[0100] Furthermore, the acid anionic group can be an acid anionic group represented by formula (A-1) or (A-2) described later, or an acid anionic group represented by any one of formulas (B-1) to (B-3) described later.

[0101] There are no particular limitations on the cationic groups in the free ionic structure. Typically, they are organic cationic groups, preferably groups with strontium or iodonium cations.

[0102] Examples of the aforementioned cationic groups include, for example, cations represented by the formula (ZaI), cations represented by the formula (ZaII), groups represented by the formula (ZBI), groups represented by the formula (ZBII), *-S+(R401)-*, or *-I+-*. * indicates the bonding position. R401 will be described later.

[0103] As described above, the anionic group in the zwitterionic structure is preferably an acidic anionic group. Specifically, examples include organic groups containing an acidic anionic group represented by formula (A-1) or (A-2) below, or organic groups containing an acidic anionic group represented by any one of formulas (B-1) to (B-3) below.

[0104] Furthermore, the acid anionic group can be an acid anionic group represented by formula (A-1) or (A-2) below, or an acid anionic group represented by any one of formulas (B-1) to (B-3) below.

[0105]

[0106] In the above formulas (A-1)~(A-2), RA represents an organic group.

[0107] * indicates the location of the bond.

[0108]

[0109] In the above equations (B-1) to (B-3), * indicates the bond position.

[0110] There is no particular limitation on the organic group represented by RA; for example, organic groups with 1 to 30 carbon atoms can be mentioned. There is no particular limitation on the organic group, but alkyl, cycloalkyl, or aryl groups are preferred.

[0111] The alkyl group is not particularly limited and can be straight-chain or branched, preferably an alkyl group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

[0112] The cycloalkyl group can be monocyclic or polycyclic, and there is no particular limitation. It is preferred to be a cycloalkyl group with 3 to 15 carbon atoms, and more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0113] There are no particular limitations on the aryl group, but it is preferred to be an aryl group with 6 to 20 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms.

[0114] The aforementioned alkyl, cycloalkyl, and aryl groups may have substituents. There are no particular limitations on the substituents, but examples of substituent T mentioned above are given. Preferably, fluorine atoms and cyano groups are used.

[0115] The cationic group in the zwitterionic structure is not particularly limited, but it is preferably an organic cationic group, and more preferably a group having strontium cation or iodonium cation.

[0116] Examples of the aforementioned cationic groups include cations represented by the formula (ZaI), cations represented by the formula (ZaII), groups represented by the formula (ZBI), groups represented by the formula (ZBII), *-S+(R401)-*, or *-I+-*. * indicates the bonding position. R401 will be described later.

[0117] Compound (I) is preferably a compound in which one or more cationic groups and two or more acidic anionic groups are covalently linked.

[0118] The cationic group in the above "one or more cationic groups" refers to a cationic group in a free ion structure or a cationic group in a zwitterionic structure.

[0119] The cationic group in the above-mentioned "one or more cationic groups" has one or more cationic groups in zwitterionic structures.

[0120] The anionic groups mentioned above in "two or more anionic groups" are anionic groups in a free ion structure or anionic groups in a zwitterionic structure.

[0121] The anionic groups in the above-mentioned "two or more anionic groups" have one or more anionic groups in zwitterionic structures.

[0122] The anionic groups in the above-mentioned "two or more anionic groups" are preferably acidic anionic groups.

[0123] When compound (I) is a compound in which one or more cationic groups and two or more anionic groups are covalently linked, there is no particular limitation on the number of cationic groups, but it is preferred to be four or less, and more preferably two or less.

[0124] When compound (I) is a compound in which one or more cationic groups and two or more anionic groups are covalently linked, the number of anionic groups is not particularly limited, but is preferably four or less, and more preferably three or less.

[0125] Compound (I) is preferably a compound in which one cationic group and two anionic groups are covalently linked.

[0126] The above-mentioned compounds are compounds having a free ionic structure and a zwitterionic structure.

[0127] Furthermore, the anionic group in the above-mentioned "two anionic groups" is preferably an acidic anionic group.

[0128] The above-mentioned ionic structure and the above-mentioned zwitterionic structure are each structures containing acid anionic groups, and preferably, compound (I) generates multiple acid groups with different pKa by irradiation with photochemical rays or radiation.

[0129] Here, compound (I) is irradiated with photochemical rays or radiation to generate a plurality of acid groups with different pKa, resulting in compound (PI) having an acid group (acid group 1) with relatively strong acid strength and an acid group (acid group 2) with relatively weak acid strength within the same compound. Acid group 1 reacts with acid-decomposing groups in the resin described later, and acid group 2 captures excess acid generated in the exposed area, thereby preventing diffusion to the unexposed area. Therefore, it is preferable to use this compound (I) because a superior pattern shape can be obtained.

[0130] The pKa of multiple acid groups produced by compound (I) by irradiation with photochemical rays or radiation is determined as follows.

[0131] (1) Consider replacing all the acid anionic groups in compound (I) with the corresponding acid groups to generate an acid-containing compound (PIA). In this case, due to the structure of compound (I), there are two possible scenarios for the acid-containing compound (PIA): one is a single compound (single molecule) with a plurality of acid groups (Case A), and the other is a plurality of compounds (plural molecules) with more than one acid group (Case B).

[0132] (2) In case A (specific example 1 can be given below), consider reducing the acid group with the lowest acid dissociation constant among the multiple acid groups in the acid-containing compound (PIA) to the corresponding acid anionic group to form an acid-containing compound (PIA-1). Calculate the pKa when the acid-containing compound (PIA) is transformed into the acid-containing compound (PIA-1), and use it as the pKa of the acid group reduced to the acid anionic group. Next, consider reducing the acid group with the lowest acid dissociation constant (if there is only one acid group) among the one or multiple acid groups in the acid-containing compound (PIA-1) to the corresponding acid anionic group to form an acid-containing compound (PIA-2). Calculate the pKa when the acid-containing compound (PIA-1) is transformed into the acid-containing compound (PIA-2), and use it as the pKa of the acid group reduced to the acid anionic group. By performing this operation until the acid groups disappear from the compound, the pKa of the complex number of acid groups in the acid-containing compound (PIA) can be determined.

[0133] Furthermore, in the above method, when there are multiple acid groups with the lowest acid dissociation constants among multiple acid groups, firstly, one of these acid groups is arbitrarily selected and the pKa is calculated when it is transformed into a compound (PIA#) that is reduced to the corresponding acid anionic group. The pKa of the remaining (unselected) acid groups is obtained by calculating the pKa when the compound (PIA#) is transformed into a compound (PIA##) that "reduces the acid groups further selected from the remaining acid groups to the corresponding acid anionic groups".

[0134] (3) In case B (specific example 2 below), determine the pKa of the acid groups of each compound when there are multiple compounds (multiple molecules) containing one or more acid groups. When a compound contains one acid group, the pKa of the acid group is obtained by reducing it to the corresponding acid anionic group. When a compound containing one or more acid groups contains multiple acid groups, the pKa of each acid group is determined according to the method described in (2) above.

[0135] (4) In the case where the acid-containing compound (PIA) contains iodocation (I+) as a constituent component of the cationic group, the above (2) and (3) are carried out by adding hydrogen atoms (I+H) to the iodocation (I+).

[0136] In the following descriptions of sample 1, sample 2, and examples, among the pKa values ​​of the plurality of acid groups obtained for the relevant compound (I), the one with the lowest acid dissociation constant (pKa) is selected and denoted as acid dissociation constant a1 (pKa1), the next lowest acid dissociation constant is selected and denoted as acid dissociation constant a2 (pKa2), and the next lowest acid dissociation constant is selected and denoted as acid dissociation constant a3 (pKa3). The acid dissociation constants are denoted in the same manner below.

[0137] Furthermore, for a complex number of acid groups with the same pKa, one of them is selected and assigned a number to its acid dissociation constant.

[0138] The measurement method for pKa will be described in detail below. The acid dissociation constant a1 (first acid dissociation constant) is less than the acid dissociation constant a2 (second acid dissociation constant).

[0139] (State 1)

[0140] As for the above compound (I), the method for determining the pKa of the two acid groups of a compound derived from a cationic group and two acid anionic groups linked by covalent bonds is described below.

[0141] The acid anionic group in the above free ionic structure is designated as A1-, and the acid anionic group in the above zwitterionic structure is designated as A2- (where the pKa (acid dissociation constant a1) of the acid group (A1H) derived from A1- is < the pKa (acid dissociation constant a2) of the acid group (A2H) derived from A2-).

[0142] In a compound (PIA) formed by replacing the counter cation of the acid anionic group represented by A1- with H+ and adding H+ to the acid anionic group represented by A2-, the pKa of the group represented by A1H is lower than that of the group represented by A2H.

[0143] The acid dissociation constants a1 and a2 are obtained by the method described above.

[0144] Furthermore, when iodocations (I+) are present in the cationic group, the acid dissociation constant is determined by adding hydrogen atoms in the form of I+H.

[0145] Once the acid dissociation constant of compound (PIA) is determined, the pKa of compound (PIA) (compound PIA is equivalent to "a compound having HA1 and HA2") when it becomes "a compound having A1- and HA2" is the acid dissociation constant a1, and the pKa of the aforementioned "compound having A1- and HA2" when it becomes "a compound having A1- and A2-" is the acid dissociation constant a2.

[0146] Furthermore, the aforementioned compound (PIA) is equivalent to an acid produced by irradiating compound (I) with photochemical rays or radiation.

[0147] The pKa (acid dissociation constant a1) of the acid group (A1H) derived from A1- is explained as < the pKa (acid dissociation constant a2) of the acid group (A2H) derived from A2-. However, when the pKa (acid dissociation constant X) of the acid group (A1H) derived from A1- is greater than the pKa (acid dissociation constant Y) of the acid group (A2H) derived from A2-, the acid dissociation constant X is the aforementioned acid dissociation constant a2, and the acid dissociation constant Y is the aforementioned acid dissociation constant a1.

[0148] When the structure of an acid anionic radical has three or more, the acid dissociation constant can be calculated sequentially in the same way as above.

[0149] (State 2)

[0150] As for the above compound (I), the following describes the method for determining the pKa of the two acid groups of a compound derived from which two cationic groups and one acidic anionic group are covalently linked and one acidic anionic group exists as a free anion (not covalently linked to the cationic group).

[0151] The acid anionic group that serves as the free anion in the above free ionic structure is designated as A1-, and the acid anionic group in the above zwitterionic structure is designated as A2- (where the pKa of the acid group (A1H) derived from A1- is taken as (acid dissociation constant Y), and the pKa of the acid group (A2H) derived from A2- is taken as (acid dissociation constant X)).

[0152] The acid dissociation constants X and Y are obtained using the method described above.

[0153] Furthermore, in zwitterionic structures, when an iodine cation (I+) is present in the cationic group, the acid dissociation constant is determined by adding hydrogen atoms in the form of I+H.

[0154] When the acid dissociation constant of the compound (PIA) derived from the above zwitterionic structure, formed by adding H+ to the acid anionic group represented by A2-, is determined, the pKa of the compound (PIIA) (compound PIA is equivalent to "a compound having HA2") becomes "a compound having A2-" is the acid dissociation constant X.

[0155] When the acid dissociation constant of a compound (PIA) derived from an acid anionic group that is the free anion mentioned above, formed by adding H+ to an acid anionic group represented by Al-, is determined, the pKa of the compound (PIA) (which is equivalent to "a compound having HA1") when it becomes "a compound having Al-" is the acid dissociation constant Y.

[0156] When comparing the acid dissociation constant X and the acid dissociation constant Y, and the acid dissociation constant X is lower than the acid dissociation constant Y, the acid dissociation constant X is the acid dissociation constant a1, and the acid dissociation constant Y is the acid dissociation constant a2.

[0157] In state 2, when free acid anionic groups are present, the acid dissociation constants of the acid (acid group) originating from the above-mentioned free acid anionic groups and the acid group originating from the zwitterionic structure are measured respectively, and the acid dissociation constants a1 and a2 are obtained by comparing their magnitudes.

[0158] For compounds with an increased number of cationic and anionic acid groups, the acid dissociation constant can also be determined in the same way.

[0159] The aforementioned ionic structure and zwitterionic structure each contain an acid anionic group. In compounds (PIA) where the aforementioned compound (I) generates multiple acid groups with different pKas through irradiation with photochemical rays or radiation, the difference between the acid dissociation constant (acid dissociation constant a1) of the acid group with the strongest acid strength (acid group A) and the acid dissociation constant (acid dissociation constant a2) of the acid group with the second strongest acid strength (acid group A) is preferably 0.70 or more, and more preferably 1.60 or more. Furthermore, there is no particular upper limit to the difference between the acid dissociation constant a1 and the acid dissociation constant a2, for example, it is 15.00 or less.

[0160] In the above compound (PIA), the acid dissociation constant a1 is not particularly limited, but is preferably -12.0 or higher.

[0161] The compound (I) is preferably a compound represented by any one of the following general formulas (I)-1 to (I)-3.

[0162]

[0163] In general formulas (I)-1 to (I)-3, A11- to A16- represent acidic anionic groups independently.

[0164] C11+~C16+ represent cationic groups independently.

[0165] L11 to L14 represent divalent organic groups independently.

[0166] L15 represents a trivalent organic group.

[0167] There are no particular limitations on the acid anionic groups of A11-, A13-~A16-, and examples of acid anionic groups represented by the following formulas (A-1) or (A-2) can be given.

[0168] In the above formulas (I)-1 to (I)-3, A11-, A13- to A16- are preferably represented independently by the acid anionic groups represented by the formulas (A-1) or (A-2) below.

[0169]

[0170] In the above general formulas (A-1)~(A-2), RA represents an organic group.

[0171] * indicates the location of the bond.

[0172] There is no particular limitation on the organic group represented by RA; for example, organic groups with 1 to 30 carbon atoms can be cited. There is no particular limitation on the organic group, but alkyl, cycloalkyl, or aryl groups are preferred.

[0173] The alkyl group is not particularly limited and can be straight-chain or branched, preferably an alkyl group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

[0174] The cycloalkyl group can be monocyclic or polycyclic, and there is no particular limitation. It is preferred to be a cycloalkyl group with 3 to 15 carbon atoms, and more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0175] There are no particular limitations on the aryl group, but it is preferred to be an aryl group with 6 to 20 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms.

[0176] The aforementioned alkyl, cycloalkyl, and aryl groups may have substituents. There are no particular limitations on the substituents, but examples of substituent T mentioned above are given. Preferably, fluorine atoms and cyano groups are used.

[0177] The acid anionic group of A12- is not particularly limited, and can be represented by any one of the following formulas (B-1) to (B-3).

[0178] In the above general formula (I)-1, A12 preferably represents an acidic anionic group represented by any one of the following formulas (B-1) to (B-3).

[0179]

[0180] In the above general formulas (B-1) to (B-3), * indicates the bond position.

[0181] There are no particular limitations on the cationic groups of C11+, C13+, and C16+; specifically, examples of organic cations can be cited.

[0182] 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)").

[0183]

[0184] In the above formula (ZaI), R201, R202 and R203 each independently represent an organic group.

[0185] The number of carbon atoms in the organic groups of R201, R202, and R203 is preferably 1 to 30, more preferably 1 to 20. Furthermore, two of R201 to R203 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 R201 to R203 include alkyl groups (e.g., butyl and pentyl) and -CH2-CH2-O-CH2-CH2-.

[0186] As preferred examples of organic cations in formula (ZaI), examples include cation (ZaI-1), cation (ZaI-2), organic cation (ZaI-3b) represented by formula (ZaI-3b), and organic cation (ZaI-4b) represented by formula (ZaI-4b).

[0187] First, the cation (ZaI-1) will be explained.

[0188] The cation (ZaI-1) is an aryl strontium cation, wherein at least one of R201 to R203 of the above formula (ZaI) is aryl.

[0189] Aryl strontium cations can be composed entirely of aryl groups (R201 to R203), or a portion of R201 to R203 can be aryl groups, with the remainder being alkyl or cycloalkyl groups.

[0190] Furthermore, a ring structure can be formed by one of R201 to R203 being an aryl group and the remaining two bonds of R201 to R203, or by including an oxygen atom, sulfur atom, ester group, amide group, or carbonyl group within the ring. Examples of groups formed by the two bonds of R201 to R203 include alkyl groups (e.g., butyl, pentyl, and -CH2-CH2-O-CH2-CH2-), wherein one or more methylene groups can be substituted with an oxygen atom, sulfur atom, ester group, amide group, and / or carbonyl group.

[0191] Examples of aryl strontium cations include triaryl strontium cations, diarylalkyl strontium cations, aryldialkyl strontium cations, diallylcycloalkyl strontium cations, and aryldicycloalkyl strontium cations.

[0192] The aryl group contained in the aryl strontium cation is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group can be a heterocyclic structure having 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.

[0193] The aryl strontium cation may have an alkyl or cycloalkyl group as desired, preferably a straight-chain alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, more preferably methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, or cyclohexyl.

[0194] The substituents that can be present in the aryl, alkyl, and cycloalkyl groups of R201 to R203 are preferably alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 14 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), cycloalkylalkoxy (e.g., 1 to 15 carbon atoms), halogen atoms (e.g., fluorine and iodine), hydroxyl, carboxyl, ester, sulfinyl, sulfonyl, alkylthio, or phenylthio.

[0195] The above-mentioned substituents may also have substituents if possible, and it is preferred that the above-mentioned alkyl group has a halogen atom as a substituent and becomes a trifluoromethyl or other haloalkyl group.

[0196] Furthermore, the aforementioned substituents are preferably formed by arbitrary combination to create acid-degradable groups.

[0197] Furthermore, the term "acid-decomposable group" refers to a group that decomposes under the action of an acid to produce a polar group. Preferably, the structure of the polar group is protected by a release group that is released under the action of an acid. The aforementioned polar group and release group are as described above.

[0198] Next, the cation (ZaI-2) will be explained.

[0199] In the cation (ZaI-2) system formula (ZaI), R201~R203 independently represent cations with organic groups that do not have aromatic rings. An aromatic ring also includes aromatic rings containing heteroatoms.

[0200] The number of carbon atoms in the non-aromatic organic groups of R201 to R203 is preferably 1 to 30, and more preferably 1 to 20.

[0201] R201 to R203 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.

[0202] Alkyl and cycloalkyl groups of R201 to R203, 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).

[0203] R201 to R203 can be further replaced by halogen atoms, alkoxy groups (e.g., carbon 1 to 5), hydroxyl groups, cyano groups, or nitro groups.

[0204] Furthermore, the substituents of R201 to R203 are preferably formed by any combination of substituents to create acid-degradable groups.

[0205] Next, the cation (ZaI-3b) will be explained.

[0206] The cation (ZaI-3b) is represented by the following formula (ZaI-3b).

[0207]

[0208] 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.

[0209] 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.

[0210] Rx and Ry independently represent alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl, or vinyl, respectively.

[0211] Furthermore, the substituents of R1c~R7c, as well as Rx and Ry, are preferably formed independently, or through any combination of substituents, into acid-degradable groups.

[0212] 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.

[0213] 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 of these rings. Examples of rings include 3 to 10-membered rings, preferably 4 to 8-membered rings, and more preferably 5 or 6-membered rings.

[0214] 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 this alkyl group can be replaced by heteroatoms such as oxygen atoms.

[0215] The group formed by the bonding of R5c with R6c and R5c with Rx is preferably a single bond or an alkyl group. Examples of alkyl groups include methylene and ethyl groups.

[0216] 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.

[0217] Next, the cation (ZaI-4b) will be explained.

[0218] The cation (ZaI-4b) is represented by the following formula (ZaI-4b).

[0219]

[0220] In equation (ZaI-4b), l represents an integer from 0 to 2.

[0221] r represents an integer from 0 to 8.

[0222] R13 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.

[0223] R14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom or 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 R14 groups, each of the above-mentioned groups, such as a hydroxyl group, represents an independent group.

[0224] R15 can independently represent alkyl, cycloalkyl, or naphthyl groups. Two R15 groups can bond together to form a ring. When two R15 groups bond together to form a ring, the ring skeleton can contain heteroatoms such as oxygen or nitrogen atoms.

[0225] In the sample, it is preferable that the two R15 groups are alkyl groups and are bonded together to form a ring structure. Furthermore, the alkyl group, the cycloalkyl group, the naphthyl group, and the ring formed by the bonded two R15 groups may have substituents.

[0226] 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 tert-butyl, etc.

[0227] Furthermore, each substituent of R13~R15, as well as Rx and Ry, is preferably formed independently, or through any combination of substituents, into an acid-decomposing group.

[0228] Next, equation (ZaII) will be explained.

[0229] In formula (ZaII), R204 and R205 independently represent aryl, alkyl, or cycloalkyl groups, respectively.

[0230] The aryl group in R204 and R205 is preferably phenyl or naphthyl, and more preferably phenyl. The aryl group in R204 and R205 can be a heterocyclic aryl group having an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocyclic aryl groups include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0231] As for the alkyl and cycloalkyl groups of R204 and R205, 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).

[0232] The aryl, alkyl, and cycloalkyl groups in R204 and R205 can each independently have substituents. Examples of substituents that can be present in the aryl, alkyl, and cycloalkyl groups of R204 and R205 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 R204 and R205 are preferably formed by any combination of substituents to create acid-degradable groups.

[0233] The following are specific examples of organic cations, but the invention is not limited thereto.

[0234]

[0235] [Chemical Formula 16]

[0236] [Chemical Formula 17]

[0237] There are no particular limitations on whether a group is a C12+ or C15+ cationic group; specifically, examples of organic cationic groups can be cited.

[0238] Among them, the organic cationic group mentioned above is preferably a group represented by formula (ZBI) or a group represented by formula (ZBII).

[0239]

[0240] In formulas (ZBI) and (ZBII), R301, R302, and R303 independently represent aryl, alkyl, or cycloalkyl groups, respectively.

[0241] R301~R302 can be bonded to form a ring structure, which can contain oxygen atoms, sulfur atoms, ester groups, amino groups or carbonyl groups.

[0242] * indicates the location of the bond.

[0243] The aryl groups of R301, R302, and R303 are preferably phenyl or naphthyl, and more preferably phenyl. The aryl groups of R301, R302, and R303 can be heterocyclic aryl groups having oxygen, nitrogen, or sulfur atoms, etc. Examples of heterocyclic aryl skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0244] The alkyl and cycloalkyl groups used in R301, R302 and R303 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).

[0245] The aryl, alkyl, and cycloalkyl groups of R301, R302, and R303 may each independently have substituents. Examples of substituents that may be present in the aryl, alkyl, and cycloalkyl groups of R301, R302, and R303 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 R301, R302, and R303 are preferably formed by any combination of substituents to create acid-degradable groups. Acid-degradable groups are described below.

[0246] R301 to R302 can be bonded to form a ring structure, and the ring may contain oxygen atoms, sulfur atoms, ester groups, amino groups or carbonyl groups. Examples of groups formed by the bonding of two of R301 to R302 include alkyl groups (e.g., butyl and pentyl) and -CH2-CH2-O-CH2-CH2-.

[0247] There are no particular limitations on the cationic groups that are C14+. Specifically, examples include *-S+(R401)-* and *-I+-*. * indicates the bond position.

[0248] R401 indicates aryl, alkyl, or cycloalkyl.

[0249] Specific examples of aryl, alkyl, and cycloalkyl groups in R401 can be given as the same as those given as aryl, alkyl, and cycloalkyl groups in R301, R302, and R303 above, and the preferred range is also the same.

[0250] The aryl, alkyl, and cycloalkyl groups of R401 can each independently have substituents. Examples of substituents that can be present in the aryl, alkyl, and cycloalkyl groups of R401 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 of R401 are preferably formed by any combination of substituents to create acid-degradable groups. Acid-degradable groups are described below.

[0251] There are no particular limitations on the divalent organic groups of L11 to L14, and examples include alkyl groups, cycloalkyl groups, aromatic cycloyl groups, aromatic heterocyclic groups, -C(=O)-, -O-, -S(=O)2-, -S-, and divalent linking groups formed by combining multiples of these.

[0252] There are no particular limitations on the alkyl group; it can be linear or branched. It is more preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 10 carbon atoms, and even more preferably an alkyl group with 1 to 3 carbon atoms.

[0253] There is no particular limitation on the cycloalkyl group, but it is preferred to be a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 10 carbon atoms, and even more preferably a cycloalkyl group with 1 to 6 carbon atoms.

[0254] There are no particular limitations on the aromatic ring group; it can be monocyclic or polycyclic. It is more preferably an aromatic ring group with 6 to 20 carbons, more preferably an aromatic ring group with 6 to 14 carbons, and even more preferably an aromatic ring group with 6 to 10 carbons.

[0255] There are no particular limitations on the aromatic heterocyclic group; it can be monocyclic or polycyclic. There are no particular limitations on the aromatic heterocyclic ring that constitutes the aromatic heterocyclic group; for example, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, etc.

[0256] Alkyl, cycloalkyl, aromatic cycloyl, and aromatic heterocyclic groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited. A fluorine atom is preferred as a substituent.

[0257] As a divalent organic group, it is preferably an enylalkyl group, an enylalkyl-O-, -O-enylalkyl group, an enylalkyl-C(=O)O-, an enylalkyl-OC(=O)-, an enylalkyl-O-enylalkyl group, or an aromatic cyclic group.

[0258] There is no particular limitation on the trivalent organic group of L15; examples include groups formed by removing a hydrogen atom from a divalent organic group.

[0259] The divalent organogroup system is the same as the divalent organogroups of L11 to L14 mentioned above, and the preferred range is also the same.

[0260] The compound represented by the above general formula (I)-1 is a compound having a free ionic structure represented by C11+A11- and an amphoteric structure represented by A12--L12-C12+.

[0261] The compounds represented by the above general formula (I)-2 are compounds having a free ionic structure represented by C13+A13- and a zwitterionic structure represented by C14+-L14-A14-.

[0262] The compounds represented by the above general formula (I)-3 are compounds having a free ionic structure represented by A16-C16+ and an amphoteric structure represented by A15--L15-C15+.

[0263] In compound PI-1, which is a compound represented by the above general formula (I)-1, wherein the counter cation of the acid anionic group represented by A11- is replaced by H+ and H+ is added to the acid anionic group represented by A12-, it is preferable that the pKa of the group represented by A11H (equivalent to the above acid dissociation constant a1) is lower than the pKa of the group represented by A12H (equivalent to the above acid dissociation constant a2).

[0264] In compound PI-2, which is a compound represented by the above general formula (I)-2, wherein the counter cation of the acid anionic group represented by A13- is replaced by H+ and H+ is added to the acid anionic group represented by A14-, it is preferable that the pKa of the group represented by A13H (equivalent to the above acid dissociation constant a1) is lower than the pKa of the group represented by A14H (equivalent to the above acid dissociation constant a2).

[0265] In compound PI-3, which is a compound represented by the above general formula (I)-3, wherein H+ is added to the acid anionic group represented by A15- and the counter cation of the acid anionic group represented by A16- is replaced by H+, it is preferable that the pKa of the group represented by A15H (equivalent to the above acid dissociation constant a1) is lower than the pKa of the group represented by A16H (equivalent to the above acid dissociation constant a2).

[0266] Specific examples of compound (I) are shown below, but the invention is not limited thereto.

[0267] [Chemical Formula 19]

[0268] [Chemical Formula 20]

[0269] The above-mentioned compound (I), as described above, is a photoacid generator, having two anionic groups (preferably acid anionic groups), and can be used both as a photoacid generator to generate the acid required for the resin reaction of the exposed section and as an acid diffusion control agent.

[0270] When compound (I) is used as a photoacid generator to generate the acid required for the resin reaction of the exposed section, and when used in combination with compound (CD), which can be used as an acid diffusion control agent as described later, it is preferable that the acid generated by compound (I) is a relatively strong acid relative to the acid generated by compound (CD).

[0271] When compound (I) is used as an acid diffusion control agent, it is preferable to use it in combination with the photoacid generator that produces the acid required for the reaction of the resin in the exposed section, which is a relatively strong acid relative to the acid produced by compound (I).

[0272] When a compound (I) has a plurality of anionic groups and the acid dissociation constants of the plurality of acid groups generated by irradiation with photochemical rays or radiation are different, a compound may contain a group that becomes a strong acid (acting as a photoacid generator) and a group that is assumed to become a weak acid relative to the group that becomes a strong acid (acting as an acid diffusion controller). In this way, a compound can function as both a photoacid generator and an acid diffusion controller.

[0273] Compound (I) can be synthesized using known methods. Specific synthetic examples of compounds represented by compound (I) will be shown in the examples described later.

[0274] The molecular weight of the above compound (I) is preferably 300-3000, more preferably 300-2000, and even more preferably 300-1500.

[0275] Compound (I) can be used alone or in combination with two or more.

[0276] In the composition of the present invention, the content of compound (I) (if there are multiple compounds, the total content thereof) is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, further preferably 5 to 25% by mass, and especially preferably 5 to 20% by mass, based on the total solid content of the composition.

[0277] <(A) Resin>

[0278] The photosensitive or radiosensitive linear resin composition (hereinafter also referred to as the "composition") preferably contains a resin (A) whose polarity increases due to decomposition by the action of acid (hereinafter also referred to as "resin (A)").

[0279] Typically, resin (A) is an acid-degradable resin, usually containing groups whose polarity increases due to decomposition by the action of acid (hereinafter also referred to as "acid-degradable groups"), preferably containing repeating units with acid-degradable groups.

[0280] Therefore, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern can be formed better, and when an organic developer is used as the developer, a negative pattern can be formed better.

[0281] As a repeating unit having an acid-decomposable group, in addition to the repeating unit having an acid-decomposable group described later, it is preferred to have a repeating unit having an acid-decomposable group containing an unsaturated bond.

[0282] (Repeating unit with acid-decomposing groups)

[0283] An acid-degradable group is a group that decomposes under the action of an acid to produce a polar group. Preferably, the acid-degradable group has a structure that protects the polar group by a release group that detaches under the action of an acid. That is, resin (A) has repeating units, and these repeating units have groups that decompose under the action of an acid to produce polar groups. Resin containing these repeating units becomes more polar under the action of an acid, thereby increasing its solubility relative to alkaline developing solutions and decreasing its solubility relative to organic solvents.

[0284] 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.

[0285] 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.

[0286] As a detaching group that is released by the action of an acid, for example, groups represented by formulas (Y1) to (Y4) can be cited.

[0287] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0288] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0289] Equation (Y3): -C(R36)(R37)(OR38)

[0290] Equation (Y4): -C(Rn)(H)(Ar)

[0291] 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 of Rx1 to Rx3 are alkyl (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl.

[0292] Wherein, Rx1 to Rx3 preferably represent straight-chain or branched alkyl groups independently, and Rx1 to Rx3 more preferably represent straight-chain alkyl groups independently.

[0293] Two of Rx1 to Rx3 can be bonded together to form a single ring or multiple rings.

[0294] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tributyl.

[0295] As for the cycloalkyl groups Rx1 to Rx3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl.

[0296] The aryl group of Rx1 to Rx3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene.

[0297] The alkenyl group of Rx1 to Rx3 is preferably vinyl.

[0298] The ring formed by the two bonds in Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by the two bonds in Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl or adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0299] The cycloalkyl group formed by two bonds in Rx1 to Rx3 may have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethyl groups constituting the cycloalkane ring may be replaced by vinylene groups.

[0300] The group represented by formula (Y1) or formula (Y2), for example, preferably Rx1 is methyl or ethyl, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0301] The photoresist composition, for example, when it is a photoresist composition for EUV exposure, is preferably formed by an alkyl group, cycloalkyl group, alkenyl group, aryl group, and two bonds of Rx1 to Rx3, and also has a fluorine atom or an iodine atom as a substituent.

[0302] In formula (Y3), R36 to R38 independently represent hydrogen atoms or monovalent organogroups. 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.

[0303] 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 replaced by heteroatoms such as oxygen atoms and / or groups containing heteroatoms such as carbonyl groups.

[0304] Furthermore, R38 can bond with other substituents in the main chain of the repeating unit to form a ring. The group formed by R38 bonding with other substituents in the main chain of the repeating unit is preferably a methylene isoalkyl group.

[0305] The photoresist composition, for example, when it is a photoresist composition for EUV exposure, preferably has a fluorine atom or an iodine atom as a substituent, formed by the monovalent organic groups represented by R36 to R38 and the ring formed by the mutual bonding of R37 and R38.

[0306] As for formula (Y3), it is preferred to be a group represented by the following formula (Y3-1).

[0307]

[0308] 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).

[0309] M represents a single-bonded or divalent linker.

[0310] 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).

[0311] 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.

[0312] 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.

[0313] At least two of Q, M, and L1 can be bonded to form a loop (preferably a 5- or 6-membered loop).

[0314] From the viewpoint of pattern refinement, 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.

[0315] When the composition of the present invention is, for example, a photosensitive or radiosensitive linear resin composition for EUV exposure, the alkyl, cycloalkyl, aryl, and groups formed by combining these groups, represented by L1 and L2, preferably also have fluorine or iodine atoms as substituents. Furthermore, in addition to fluorine and iodine atoms, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups preferably also contain heteroatoms such as oxygen atoms (that is, for example, one of the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups, a methylene group, is replaced by a heteroatom such as an oxygen atom, or a group containing heteroatoms such as a carbonyl group).

[0316] Furthermore, when the composition of the present invention is, for example, a photoresist composition for EUV exposure, the heteroatom is preferably selected from the group consisting of alkyl groups that may contain heteroatoms represented by Q, cycloalkyl groups that may contain heteroatoms, aryl groups, amino groups, ammonium groups, mercapto groups, cyano groups, aldehyde groups that may contain heteroatoms, and groups composed of combinations thereof.

[0317] 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.

[0318] When the composition of the present invention is, for example, a photoresist composition for EUV exposure, the aromatic cyclic group represented by Ar and the alkyl, cycloalkyl and aryl groups represented by Rn are preferably substituents having fluorine or iodine atoms.

[0319] From the viewpoint of excellent acid decomposition properties of repeating units, in the detachment 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 in the non-aromatic ring that is directly bonded to the polar group (or its residue) is preferably not a halogen atom such as a fluorine atom as a substituent.

[0320] In addition, the detaching group that is released by the action of acid can also be 2-cyclopentenyl with a substituent (alkyl, etc.) such as 3-methyl-2-cyclopentenyl, and cyclohexyl with a substituent (alkyl, etc.) such as 1,1,4,4-tetramethylcyclohexyl.

[0321] As a repeating unit with an acid-decomposable group, it is also preferred to be a repeating unit represented by formula (A).

[0322]

[0323] 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 removed by the action of an acid. At least one of L1, R1, and R2 has a fluorine or iodine atom.

[0324] L1 represents a divalent linker that may have a fluorine atom or an iodine atom. Examples of divalent linkers that may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that may have a fluorine atom or an iodine atom (e.g., alkylene, cycloalkylene, alkenylene, and arylene), and linkers formed by the linkage of multiple such groups. Among these, L1 is preferably -CO-, arylene, or an alkylene group having a -arylene-fluorine atom or an iodine atom, and more preferably -CO- or an alkylene group having a -arylene-fluorine atom or an iodine atom.

[0325] As an enfrylene group, enfrylene is preferred.

[0326] 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 preferably 1 to 10, and more preferably 1 to 3.

[0327] 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.

[0328] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine atom or an iodine atom, or an aryl group that may have a fluorine atom or an iodine atom.

[0329] Alkyl groups 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.

[0330] 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 preferred to be 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0331] The aforementioned alkyl groups may contain heteroatoms such as oxygen atoms in addition to halogen atoms.

[0332] R2 represents a detaching group that is released by the action of an acid and may have a fluorine atom or an iodine atom. Examples of detaching groups that may have a fluorine atom or an iodine atom include those represented by the above formulas (Y1) to (Y4) and have a fluorine atom or an iodine atom.

[0333] As a repeating unit with an acid-decomposable group, it is preferably a repeating unit represented by formula (AI).

[0334]

[0335] In formula (AI), Xa1 represents a hydrogen atom or an alkyl group that may have substituents. T represents a single bond or a divalent linker. Rx1 to Rx3 independently represent alkyl (linear or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (linear or branched), or aryl (monocyclic or polycyclic). Preferably, when all of Rx1 to Rx3 are alkyl (linear or branched), at least two of Rx1 to Rx3 are methyl groups.

[0336] Two of Rx1 to Rx3 can bond together to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0337] As represented by Xa1, an alkyl group that can have substituents, examples include methyl or a group represented by -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 Xa1, a hydrogen atom, methyl, trifluoromethyl, or hydroxymethyl is preferred.

[0338] 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.

[0339] 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.

[0340] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0341] As for the cycloalkyl groups Rx1 to Rx3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl.

[0342] The aryl group of Rx1 to Rx3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene.

[0343] The alkenyl group of Rx1 to Rx3 is preferably vinyl.

[0344] The cycloalkyl group formed by two bonds in Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. More preferably, it is a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, or adamantyl. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.

[0345] 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.

[0346] The repeating unit represented by formula (AI), for example, preferably Rx1 is methyl or ethyl, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl state.

[0347] 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.

[0348] As the repeating unit represented by formula (AI), it is preferably an acid-degradable (meth)acrylate trialkyl ester repeating unit (Xa1 represents a hydrogen atom or methyl group, and T represents a single bond repeating unit).

[0349] Specific examples of repeating units having acid-decomposable groups are shown below, but the present invention is not limited thereto. 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.

[0350] [Chemical Formula 24]

[0351]

[0352] [Chemical Formula 26]

[0353]

[0354] [Chemical Formula 28]

[0355] Resin (A), as a repeating unit with an acid-degradable group, may have repeating units containing an acid-degradable group with an unsaturated bond.

[0356] As a repeating unit having an acid-decomposing group containing an unsaturated bond, it is preferably a repeating unit represented by formula (B).

[0357] [Chemical Formula 29]

[0358] 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. Ry1 to Ry3 independently represent linear or branched alkyl groups, monocyclic or polycyclic cycloalkyl groups, alkenyl groups, alkynyl groups, or monocyclic or polycyclic aryl groups. At least one of Ry1 to Ry3 represents an alkenyl group, alkynyl group, monocyclic or polycyclic cycloalkenyl group, or monocyclic or polycyclic aryl group.

[0359] Two of Ry1 to Ry3 can bond together to form monocyclic or polycyclic rings (monocyclic or polycyclic cycloalkyl, cycloalkenyl, etc.).

[0360] As represented by Xb, an alkyl group that can have substituents, examples include methyl or a group represented by -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.

[0361] 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.

[0362] The L group is preferably -Rt-, -CO-, -COO-Rt-CO-, or -Rt-CO-. Rt may have substituents such as halogen atoms, hydroxyl groups, or alkoxy groups. An aromatic group is preferred.

[0363] The alkyl groups of Ry1 to Ry3 are preferably alkyl groups with 1 to 4 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0364] As for the cycloalkyl groups of Ry1 to Ry3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl.

[0365] The aryl group of Ry1 to Ry3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene.

[0366] The alkenyl group of Ry1 to Ry3 is preferably vinyl.

[0367] The acetylenic group of Ry1 to Ry3 is preferably acetylenic.

[0368] The cycloalkenyl groups of Ry1 to Ry3 are preferably those containing double bonds as part of a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl.

[0369] The cycloalkyl group formed by two bonds in Ry1 to Ry3 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.

[0370] Cycloalkyl or cycloalkenyl groups formed by two bonds in Ry1 to Ry3, 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 group containing a heteroatom such as a -SO2- group or an SO3- group, a vinylidene group, 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 vinylidenes.

[0371] The repeating unit represented by formula (B), for example, preferably Ry1 is methyl, ethyl, vinyl, allyl, or aryl, and Ry2 and Ry3 are bonded to form the above-mentioned cycloalkyl or cycloalkenyl state.

[0372] 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.

[0373] 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).

[0374] 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 particularly preferably 60 mol% or less, relative to all repeating units in resin (A).

[0375] Specific examples of repeating units having acid-decomposing groups containing unsaturated bonds are shown below, but the present invention is 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 group (-OCOR''' or -COOR''': R''' is an alkyl or fluoroalkyl group 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 and m represent integers greater than or equal to 0.

[0376] [Chemical Formula 30]

[0377] [Chemical Formula 31]

[0378] [Chemical Formula 32]

[0379] [Chemical Formula 33]

[0380] Resin (A) may contain only one repeating unit with an acid-degradable group, or it may contain two or more repeating units at the same time.

[0381] 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.

[0382] 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.

[0383] Group A is a group consisting of repeating units of the following (20) to (29).

[0384] (20) The repeating unit with acid groups, described later.

[0385] (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.

[0386] (22) Repeating units having lactone, sulcinolone, or carbonate groups, as described later.

[0387] (23) The repeating unit with photoacid-generating group described later.

[0388] (24) Repeating units described later, represented by equation (V-1) or equation (V-2) below.

[0389] (25) The repeating unit, referred to later by equation (A),

[0390] (26) The repeating unit, referred to later by equation (B),

[0391] (27) The repeating unit, referred to later by equation (C),

[0392] (28) The repeating unit, referred to later by equation (D),

[0393] (29) The repeating unit, referred to later by equation (E),

[0394] Group B is a group consisting of repeating units of the following (30) to (32).

[0395] (30) The repeating unit described below, having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano, and base-soluble group.

[0396] (31) The repeating unit described later, which has an alicyclic hydrocarbon structure and does not exhibit acid decomposition properties.

[0397] (32) The repeating unit described later, which does not have either a hydroxyl or a cyano group, and is represented by formula (III).

[0398] Resin (A) preferably has acid groups, and as described below, preferably comprises 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.

[0399] When the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for EUV, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above-mentioned group A.

[0400] Furthermore, when the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for EUV, 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 a repeating unit containing both fluorine atoms and iodine atoms, or resin (A) may contain both repeating units containing fluorine atoms and repeating units containing iodine atoms.

[0401] Furthermore, when the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for EUV, the resin (A) is preferably a resin having repeating units containing aromatic groups.

[0402] When the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above-mentioned group B.

[0403] Furthermore, when the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for ArF, the resin (A) is preferably free of either fluorine atoms or silicon atoms.

[0404] Furthermore, when the composition of the present invention is used as a photosensitive or radiosensitive linear resin composition for ArF, the resin (A) preferably does not have aromatic groups.

[0405] (Repeating units with acid groups)

[0406] Resin (A) may have repeating units containing acid groups.

[0407] 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.

[0408] 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 generally 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.

[0409] 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.

[0410] Furthermore, in the aforementioned hexafluoroisopropanol group, one or more (preferably one to two) fluorine atoms can be replaced 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 replaced by groups other than fluorine atoms to form a ring containing -C(CF3)(OH)-CF2-.

[0411] The repeating unit having an acid group is preferably a repeating unit that is different from repeating units having a structure that protects the polar group by a release group that is released by the action of the acid described above, and repeating units having lactone, sulcinolone or carbonate groups as described later.

[0412] Repeating units with acid groups can have fluorine or iodine atoms.

[0413] The following repeating units can be cited as examples of repeating units having acid groups.

[0414]

[0415] As a repeating unit having an acid group, it is preferably a repeating unit represented by the following formula (1).

[0416] [Chemical Formula 35]

[0417] 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, alkylsulfonyl, alkoxycarbonyl, or aryloxycarbonyl, and when there are multiple Rs, they can be the same or different. 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).

[0418] The following examples illustrate repeating units with acid groups. In the formula, a represents 1 or 2.

[0419]

[0420] [Chemical Formula 37]

[0421]

[0422] [Chemical Formula 39]

[0423] Furthermore, among the repeating units described above, the repeating units are preferably those specifically described below. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0424]

[0425] [Chemical Formula 41]

[0426] 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).

[0427] (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)

[0428] 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. Furthermore, the <repeating units with fluorine, bromine, or iodine atoms that do not have either acid-decomposable groups or acid groups> mentioned here are preferably other types of repeating units belonging to group A, different from the <repeating units with lactone, sulopentalide, or carbonate groups> and <repeating units with photoacid-generating groups> described later.

[0429] As unit X, it is preferably a repeating unit represented by equation (C).

[0430]

[0431] L5 represents a single bond or an ester group. R9 represents an alkyl group that may have a hydrogen atom, or a fluorine atom, or an iodine atom. R10 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.

[0432] The following examples illustrate repeating units having fluorine or iodine atoms.

[0433]

[0434] The content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to all repeating units in resin (A). Furthermore, as an upper limit, it is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, relative to all repeating units in resin (A).

[0435] 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).

[0436] Furthermore, as a repeating unit 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.

[0437] (Repeating units with lactone, sulcinolone, or carbonate groups)

[0438] Resin (A) may have at least one repeating unit (hereinafter also referred to as "unit Y") selected from the group consisting of lactone groups, sulcinolone groups and carbonate groups.

[0439] Unit Y is also preferably free of acid groups such as hydroxyl and hexafluoropropanol groups.

[0440] As a lactone or sulfonyl group, it is sufficient to have a lactone or sulfonyl structure. The lactone or sulfonyl structure is preferably a 5-7 membered ring lactone or 5-7 membered ring sulfonyl structure. More preferably, it is a bicyclic or spirocyclic structure formed by ring condensation of other ring structures on the 5-7 membered ring lactone structure, or a bicyclic or spirocyclic structure formed by ring condensation of other ring structures on the 5-7 membered ring sulfonyl structure.

[0441] Resin (A) is preferably a repeating unit containing a lactone group or a sulfonolactone group, wherein the lactone group or sulfonolactone group is formed by extracting 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 sulfonolactone structure represented by any one of the following formulas (SL1-1) to (SL1-3).

[0442] Furthermore, lactone or sulfonyl groups can also be directly bonded to the main chain. For example, the ring-membered atoms of lactone or sulfonyl groups can also form the main chain of resin (A).

[0443] [Chemical Formula 44]

[0444] The aforementioned lactone or sulopentalide structures can also have substituents (Rb2). Preferred substituents (Rb2) include alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 4 to 7 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 1 to 8 carbon atoms, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, the plurality of Rb2 groups can be different, and the plurality of Rb2 groups can bond together to form a ring.

[0445] As a repeating unit having a group comprising 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.

[0446]

[0447] In formula (AI), Rb0 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 Rb0 include hydroxyl groups and halogen atoms.

[0448] Examples of halogen atoms that can be represented by Rb0 include fluorine, chlorine, bromine, and iodine. Rb0 is preferably represented by hydrogen or methyl.

[0449] 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 group composed of combinations thereof. Preferably, Ab is a single bond or a linker represented by -Ab1-CO2-. Ab1 is a straight-chain or branched alkyl group, or a monocyclic or polycyclic cycloalkyl group, preferably methylene, ethyl, cyclohexyl, adamantyl, or norbornenyl.

[0450] 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).

[0451] When an optical isomer exists in a repeating unit containing a lactone or sulopentalide group, any optical isomer can be used. Furthermore, a single optical isomer can be used alone, or multiple optical isomers can be used in combination. When primarily using one optical isomer, its optical purity (ee) is preferably 90% or higher, and more preferably 95% or higher.

[0452] As a carbonate group, a cyclic carbonate group is preferred.

[0453] As a repeating unit having a cyclic carbonate group, it is preferably a repeating unit represented by the following formula (A-1).

[0454]

[0455] 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 distinct. 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 group formed by combining these. Z represents a group that, together with the group represented by -O-CO-O- in the formula, forms a monocyclic or polycyclic ring.

[0456] The following example illustrates unit Y.

[0457]

[0458] [Chemical Formula 48]

[0459]

[0460] The content of unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, relative to all repeating units in resin (A). Furthermore, as an upper limit, 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, relative to all repeating units in resin (A).

[0461] (Repeating unit with photoacid-generating group)

[0462] 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").

[0463] As a repeating unit containing a photoacid generating group, the repeating unit represented by equation (4) can be cited.

[0464]

[0465] R41 represents a hydrogen atom or a methyl group. L41 represents a single bond or a divalent linker. L42 represents a divalent linker. R40 represents a structural site where acid is produced in the side chain due to decomposition caused by photochemical irradiation or radiation.

[0466] The following are examples of repeating units having photoacid-generating groups.

[0467]

[0468] 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.

[0469] 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).

[0470] (Repeating units represented by equation (V-1) or equation (V-2) below)

[0471] Resin (A) may have repeating units represented by the following formula (V-1) or the following formula (V-2).

[0472] 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 mentioned above.

[0473]

[0474] 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.

[0475] n3 represents an integer from 0 to 6.

[0476] n4 represents an integer from 0 to 4.

[0477] X4 represents a methylene group, an oxygen atom, or a sulfur atom.

[0478] The following examples illustrate repeating units represented by equations (V-1) or (V-2).

[0479] 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.

[0480] (Repetitive units used to reduce the mobility of the main chain)

[0481] 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.

[0482] 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 the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of these is taken as the Tg (°C) of the polymer.

[0483] The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). Furthermore, when calculating Tg using the Bicerano method, the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.) can be used.

[0484] 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). As a method to reduce the mobility of the main chain of resin (A), the following methods (a) to (e) can be cited.

[0485] (a) Introducing large-volume substituents into the main chain

[0486] (b) Introducing multiple substituents into the main chain

[0487] (c) Introducing substituents into the vicinity of the main chain to induce interactions between resins (A).

[0488] (d) Formation of the main chain in the ring structure

[0489] (e) Linking ring structures to the main chain

[0490] Furthermore, resin (A) is preferably a repeating unit having a Tg of 130°C or higher as a homopolymer.

[0491] 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 types of functional groups in the repeating units represented by equations (A) to (E) described later can be used to identify repeating units whose Tg of the homopolymer is above 130°C.

[0492] 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.

[0493]

[0494] 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, which may or may not be fused together.

[0495] 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.

[0496] 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.

[0497]

[0498] In formula (B), Rb1 to Rb4 independently represent hydrogen atoms or organic groups, and at least two of Rb1 to Rb4 represent organic groups.

[0499] Furthermore, when at least one of the organic groups is a group that is directly linked to the main chain in the ring structure and repeating unit, there are no particular restrictions on the types of other organic groups.

[0500] Furthermore, when there is no group in the organic group that is a ring structure directly linked to the main chain in the repeating unit, at least two of the organic groups are substituents with a number of three or more constituent atoms other than hydrogen atoms.

[0501] 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.

[0502] 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.

[0503]

[0504] 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 at a number of atoms up to 3 in the main chain. Preferably, for inducing the interaction between the main chains of resin (A), hydrogen atoms with hydrogen bonding at a number of atoms up to 2 (closer to the main chain) are preferred.

[0505] 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.

[0506] 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.

[0507] [Chemical Formula 56]

[0508] 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.

[0509] 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.

[0510] 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.

[0511]

[0512] 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.

[0513] "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.

[0514] 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.

[0515] (A repeating unit having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano, and base-soluble groups)

[0516] Resin (A) may have repeating units containing at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano and base-soluble groups.

[0517] 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>.

[0518] Resin (A) may have repeating units containing hydroxyl or cyano groups. This improves substrate adhesion and developer affinity.

[0519] 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.

[0520] 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.

[0521] Resin (A) may have repeating units containing base-soluble groups.

[0522] 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), the resolving power 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.

[0523] (A repeating unit with an alicyclic hydrocarbon structure that does not exhibit acid decomposition properties)

[0524] Resin (A) may contain repeating units with an alicyclic hydrocarbon structure that do not exhibit acid decomposition properties. This reduces the leaching of low-molecular-weight components from the photoresist film into the immersion solution during immersion exposure. Examples of such repeating units include those derived from 1-adamantane (meth)acrylate, diadamantane (meth)acrylate, tricyclodecyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0525] (A repeating unit represented by formula (III) that does not have either a hydroxyl or a cyano group)

[0526] Resin (A) may have repeating units represented by formula (III) that do not have either hydroxyl or cyano groups.

[0527]

[0528] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and not having either a hydroxyl or a cyano group.

[0529] 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.

[0530] 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.

[0531] (Other repeating units)

[0532] Furthermore, resin (A) may have repeating units other than the repeating units described above.

[0533] For example, resin (A) may have repeating units selected from the group consisting of repeating units having an oxacyclic group, repeating units having an oxazolone cyclic group, repeating units having a dioxane cyclic group, and repeating units having a hydantoin cyclic group.

[0534] The following are examples of this type of repeating unit.

[0535]

[0536] In addition to the repeating structural units mentioned above, resin (A) can also have various repeating structural units to adjust dry etching resistance, standard developer compatibility, substrate adhesion, photoresist shape, resolution, heat resistance, and sensitivity.

[0537] As resin (A), it is preferable that all repeating units (especially when the composition is used as a photosensitive or radiosensitive linear resin composition for ArF) are composed of repeating units derived from compounds having vinyl unsaturated bonds. In particular, it is also preferable that all repeating units are composed of (meth)acrylate repeating units. In this case, it is permissible to use a composition in which all repeating units are methacrylate repeating units, all repeating units are acrylate repeating units, or all repeating units are derived from either methacrylate repeating units or acrylate repeating units, with the acrylate repeating units being preferably 50 moles or less of all repeating units.

[0538] Resin (A) can be synthesized using conventional methods (such as free radical polymerization).

[0539] Using the GPC method with polystyrene equivalents, the weight average molecular weight of resin (A) is preferably below 30,000, more preferably 1,000 to 30,000, further preferably 3,000 to 30,000, and especially preferably 5,000 to 15,000.

[0540] The dispersion (molecular weight distribution) 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.

[0541] In the photoresist 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 composition.

[0542] Resin (A) can be used in one form or in combination with other forms.

[0543] <Photoacid generator>

[0544] The composition of the present invention may include a photoacid generator (B) that is not equivalent to the above-described compound (I).

[0545] Photoacid generator (B) is a compound that generates the acid required for the resin reaction in the exposed section.

[0546] 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).

[0547] 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.

[0548] 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).

[0549] In this invention, the photoacid generator (B) is preferably in the form of a low molecular weight compound.

[0550] 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.

[0551] 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.

[0552] In compounds represented by "M+X-", M+ represents an organic cation.

[0553] There are no particular restrictions on whether an organic cation can be monovalent or divalent or higher.

[0554] There is no particular limitation on the organic cation, but it is preferred to be a cation represented by the above formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by the above formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0555] In compounds represented by "M+X-", X- represents an organic anion.

[0556] There are no particular limitations on what constitutes an organic anion; examples of organic anions with a valence of one or more valences can be given.

[0557] As an organic anion, it is preferably an anion with very low ability to induce nucleophilic reactions, and more preferably a non-nucleophilic anion.

[0558] 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.

[0559] 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.

[0560] 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).

[0561] 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.

[0562] 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.

[0563] The aralkyl group in the aralkyl carboxylic acid anion is preferably an aralkyl group with 7 to 14 carbon atoms.

[0564] Examples of aryl alkyl groups having 7 to 14 carbon atoms include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl.

[0565] Examples of sulfadiazine anions include, for instance, saccharin anion.

[0566] 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.

[0567] Furthermore, the alkyl groups in the bis(alkylsulfonyl)imidin anion can also bond with each other to form a ring structure. This increases the acid strength.

[0568] Other nonnucleophilic anions include, for example, phosphorus fluoride (e.g., PF6-), boron fluoride (e.g., BF4-), and antimony fluoride (e.g., SbF6-).

[0569] 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.

[0570] As a non-nucleophilic anion, it is also preferred to be an anion represented by the following formula (AN1).

[0571]

[0572] In formula (AN1), R1 and R2 independently represent hydrogen atoms or substituents, respectively.

[0573] 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.

[0574] Furthermore, the non-electron-withdrawing groups are preferably, independently, -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0575] 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.

[0576] R1 and R2 are each, independently, preferably, a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0577] L represents a divalent linker.

[0578] When there are multiple Ls, each L can be the same or different.

[0579] Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining a plurality of these. Among these, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene-, -COO-alkylene-, or -CONH-alkylene- are preferred, and more preferably -O-CO-O-, -O-CO-O-alkylene-, -COO-, -CONH-, -SO2-, or -COO-alkylene-.

[0580] L, for example, is preferably a group represented by the following formula (AN1-1).

[0581] *a-(CR2a2)xQ-(CR2b2)Y-*b (AN1-1)

[0582] In equation (AN1-1), *a represents the bond position with R3 in equation (AN1).

[0583] *b indicates the bond position with -C(R1)(R2)- in equation (AN1).

[0584] X and Y represent integers from 0 to 10, preferably integers from 0 to 3.

[0585] R2a and R2b represent hydrogen atoms or substituents independently, respectively.

[0586] When there are multiple R2a and R2b respectively, the multiple R2a and R2b can be the same or different.

[0587] Among them, when Y is 1 or above, the R2b atom in CR2b2 that is directly bonded to -C(R1)(R2)- in formula (AN1) is a non-fluorine atom.

[0588] Q represents *AO-CO-O-*B, *A-CO-*B, *A-CO-O-*B, *AO-CO-*B, *AO-*B, *AS-*B, or *A-SO2-*B.

[0589] Where X+Y in formula (AN1-1) is 1 or more and all of R2a and R2b in formula (AN1-1) are hydrogen atoms, Q represents *AO-CO-O-*B, *A-CO-*B, *AO-CO-*B, *AO-*B, *AS-*B, or *A-SO2-*B.

[0590] *A represents the bond position on the R3 side in equation (AN1), and *B represents the bond position on the -SO3- side in equation (AN1).

[0591] In formula (AN1), R3 represents an organic group.

[0592] 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.).

[0593] 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).

[0594] Organic groups having the above-mentioned cyclic structure may, for example, have or not have heteroatoms (oxygen atoms, sulfur atoms, and / or nitrogen atoms, etc.). Heteroatoms may be replaced by one or more carbon atoms forming the cyclic structure.

[0595] 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.

[0596] The hydrocarbon group having the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents.

[0597] 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.

[0598] As the above-mentioned lactone group and sulfonolactone group, for example, in any of the structures represented by the above formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3), 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.

[0599] As a non-nucleophilic anion, it can be a benzenesulfonic acid anion, preferably a benzenesulfonic acid anion substituted with branched alkyl or cycloalkyl groups.

[0600] As a non-nucleophilic anion, it is also preferred to be an anion represented by the following formula (AN2).

[0601]

[0602] 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.

[0603] 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. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0604] 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 of which have Xf as fluorine atoms.

[0605] 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 can be the same or different.

[0606] The alkyl groups represented by R4 and R5 are preferably 1 to 4 carbon atoms. These alkyl groups may have substituents. Hydrogen atoms are preferably present as R4 and R5.

[0607] L represents a binary linking basis. The definition of L is synonymous with L in equation (AN1).

[0608] W represents an organic group containing a cyclic structure. Preferably, it is a cyclic organic group.

[0609] Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups.

[0610] 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.

[0611] The aryl group can be monocyclic or polycyclic. Examples of the aforementioned aryl groups include phenyl, naphthyl, phenanthryl, and anthracene.

[0612] The heterocyclic group can be monocyclic or polycyclic. When it is a polycyclic heterocyclic group, it can further suppress acid diffusion. Furthermore, the heterocyclic group can be aromatic or non-aromatic. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocycles include tetrahydropyran rings, lactone rings, sulfonyl lactone rings, and decahydroisoquinoline rings. Preferably, the heterocycle in the heterocyclic group is a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0613] 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.

[0614] The preferred anions represented by formula (AN2) are SO3--CF2-CH2-OCO-(L)q'-W, SO3--CF2-CHF-CH2-OCO-(L)q'-W, SO3--CF2-COO-(L)q'-W, SO3--CF2-CF2-CH2-CH2-(L)qW, or SO3--CF2-CH(CF3)-OCO-(L)q'-W. Here, L, q, and W are the same as in formula (AN2). q' represents an integer from 0 to 10.

[0615] As a non-nucleophilic anion, it is also preferred to be an aromatic sulfonic acid anion represented by the following formula (AN3).

[0616]

[0617] 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.

[0618] 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.

[0619] 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.

[0620] B represents a hydrocarbon group.

[0621] 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.

[0622] As a non-nucleophilic anion, disulfonamide anion is also preferred.

[0623] For example, the disulfonamide anion is an anion represented by N-(SO2-Rq)2.

[0624] Here, Rq represents an alkyl group that may have substituents, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. Two Rq groups may bond together to form a ring. The group formed by the bonding of two Rq 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.

[0625] Furthermore, as non-nucleophilic anions, anions represented by the following formulas (d1-1) to (d1-4) can also be cited.

[0626]

[0627]

[0628] In formula (d1-1), R51 represents a hydrocarbon group (e.g., aryl, such as phenyl) that may have substituents (e.g., hydroxyl).

[0629] In formula (d1-2), Z2c 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).

[0630] The hydrocarbon group in Z2c 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.

[0631] Furthermore, "Z2c-SO3-" in formula (d1-2) is preferably different from the anion represented by formulas (AN1) to (AN3) above. For example, Z2c is preferably something other than an aryl group. Also, for example, the atoms at the α and β positions relative to -SO3- in Z2c are preferably atoms other than carbon atoms having fluorine atoms as substituents. For example, the atoms at the α position and / or β position relative to -SO3- in Z2c are preferably ring-membered atoms in a cyclic group.

[0632] 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.

[0633] 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.

[0634] Organic anions can be used alone or in combination with two or more.

[0635] The photoacid generator is preferably selected from at least one of the group consisting of compounds (1) to (2).

[0636] (Compound(1))

[0637] Compound (1) is a compound having one or more of the following structural sites X and one or more of the following structural sites Y, and is a compound containing an acid derived from the following first acidic site derived from the following structural site X and the following second acidic site derived from the following structural site Y by irradiation with photochemical rays or radiation.

[0638] Structural site X: Composed of anionic site A1- and cationic site M1+, and formed by irradiation with photochemical rays or radiation, forming a first acidic site represented by HA1.

[0639] 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.

[0640] Furthermore, the above compound (1) satisfies the following condition I.

[0641] Condition I: In the above compound (1), the compound PI obtained by replacing the above cation M1+ in the above structural site X and the above cation M2+ in the above structural site Y with H+ has an acid dissociation constant a1 derived from the acidic site represented by HA1, which is obtained by replacing the above cation M1+ in the above structural site X with H+, and an acid dissociation constant a2 derived from the acidic site represented by HA2, which is obtained by replacing the above cation M2+ in the above structural site Y with H+, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0642] The following will provide a more detailed explanation of condition I.

[0643] When compound (1), for example, is 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, compound PI is equivalent to "a compound having HA1 and HA2".

[0644] More specifically, given the acid dissociation constants a1 and a2 of compound PI, when compound PI is determined, the pKa of compound PI as "a compound having A1- and HA2" is the acid dissociation constant a1, and the pKa of the aforementioned "compound having A1- and HA2" as "a compound having A1- and A2-" is the acid dissociation constant a2.

[0645] Furthermore, when compound (1), for example, is to produce an acid having two first acidic sites derived from the above-mentioned structural site X and one second acidic site derived from the above-mentioned structural site Y, compound PI is equivalent to "a compound having two HA1 and one HA2".

[0646] Having determined the acid dissociation constant of compound PI, the acid dissociation constant when compound PI is a "compound having one Al-, one HA1, and one HA2", and the acid dissociation constant when the "compound having one Al-, one HA1, and one HA2" becomes a "compound having two Al- and one HA2", are equivalent to the aforementioned acid dissociation constant a1. Furthermore, the acid dissociation constant when the "compound having two Al- and one HA2" becomes a "compound having two Al- and A2-" is equivalent to the acid dissociation constant a2. That is, in the case of compound PI, when there are multiple acid dissociation constants for the acidic site represented by HA1, which is formed by replacing the cation M1+ in 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 PI is defined as "aa" when it is "a compound having one Al-, one HA1, and one HA2", and the acid dissociation constant of "a compound having one Al-, one HA1, and one HA2" is defined as "ab" when it is "a compound having two Al- and one HA2", the relationship between aa and ab satisfies aa <ab。

[0647] The acid dissociation constants a1 and a2 are determined by the above-mentioned method for determining the acid dissociation constant.

[0648] The above compound PI is equivalent to the acid produced when compound (1) is irradiated by photochemical rays or radiation.

[0649] When compound (1) has two or more structural sites X, the structural sites X can be the same or different. Also, two or more of the above-mentioned Al- and two or more of the above-mentioned M1+ can be the same or different.

[0650] Furthermore, in compound (1), 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.

[0651] In the aforementioned compound PI, 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.

[0652] In the above-mentioned compound PI, 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.

[0653] Furthermore, in the above-mentioned compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. In addition, as a lower limit value of the acid dissociation constant a1, it is preferably -20.0 or more.

[0654] 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.

[0655] The anionic site A1- is preferably an anionic site capable of forming an acidic site with a small 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).

[0656] Furthermore, the anionic site A2- is preferably an acidic site capable of forming 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).

[0657] Furthermore, in the following equations (AA-1) to (AA-3) and (BB-1) to (BB-6), * indicates the bond position.

[0658] 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.

[0659]

[0660] Furthermore, the cation sites M1+ and M2+ are structural sites containing positively charged atoms or groups of atoms; for example, monovalent organic cations can be cited. In addition, organic cations represented by M+ as described above can be cited as examples of organic cations.

[0661] There are no particular restrictions on the specific structure of compound (1). For example, compounds represented by formulas (Ia-1) to (Ia-5) described later can be cited.

[0662] -Compounds represented by formula (Ia-1)-

[0663] The following section will first describe the compound represented by formula (Ia-1).

[0664] M11+A11--L1-A12-M12+ (Ia-1)

[0665] The compound represented by formula (Ia-1) produces an acid represented by HA11-L1-A12H when exposed to photochemical rays or radiation.

[0666] In formula (Ia-1), M11+ and M12+ independently represent organic cations, A11- and A12- independently represent monovalent anionic functional groups, and L1 represents a divalent linker.

[0667] M11+ and M12+ can be the same or different.

[0668] A11- and A12- can be the same or different, but it is better if they are different from each other.

[0669] However, in the above formula (Ia-1), in the compound PIa (HA11-L1-A12H) formed by replacing the cations represented by M11+ and M12+ with H+, the acid dissociation constant a2 derived from the acidic site represented by A12H is greater than the acid dissociation constant a1 derived from the acidic site represented by HA11. Furthermore, the preferred values ​​of the acid dissociation constants a1 and a2 are as described above. Also, compound PIa is the same acid as the acid produced by the compound represented by formula (Ia-1) through irradiation with photochemical rays or radiation.

[0670] Furthermore, at least one of M11+, M12+, A11-, A12- and L1 may have an acid-decomposable group as a substituent.

[0671] In formula (Ia-1), as organic cations represented by M11+ and M12+, examples of organic cations represented by M+ as described above can be given.

[0672] The term "monovalent anionic functional group represented by A11-" refers to a group containing the aforementioned anionic site A1- and is monovalent. Similarly, the term "monovalent anionic functional group represented by A12-" refers to a group containing the aforementioned anionic site A2- and is monovalent.

[0673] The monovalent anionic functional group represented by A11- and A12- is preferably a monovalent anionic functional group containing the anionic site 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). Furthermore, as a monovalent anionic functional group represented by A12-, it is preferably a monovalent anionic functional group represented by any one of formulas (BX-1) to (BX-7), and more preferably a monovalent anionic functional group represented by any one of formulas (BX-1) to (BX-6).

[0674]

[0675] In equations (AX-1) to (AX-3), RA1 and RA2 independently represent monovalent organic groups. * indicates the bond position.

[0676] There are no particular limitations on the monovalent organic group represented by RA1; for example, cyano, trifluoromethyl, and methanesulfonyl can be cited.

[0677] As a monovalent organic group represented by RA2, it is preferably a straight-chain, branched, or cyclic alkyl or aryl group.

[0678] 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.

[0679] 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.

[0680] The aryl group is preferably phenyl or naphthyl, and more preferably phenyl.

[0681] 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.

[0682] In equations (BX-1) to (BX-4) and (BX-6), RB represents a monovalent organic group. * indicates a bond position.

[0683] As a monovalent organic group represented by RB, it is preferably a straight-chain, branched, or cyclic alkyl group or an aryl group.

[0684] 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.

[0685] 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 described above has a fluorine atom as a substituent, it may also be a perfluoroalkyl group.

[0686] Furthermore, when the carbon atom in the alkyl group that becomes the bonding position (for example, in the cases of formulas (BX-1) and (BX-4), it is equivalent to a carbon atom directly bonded to the -CO- group explicitly stated in the formula in the alkyl group; in the cases of formulas (BX-2) and (BX-3), it is equivalent to a carbon atom directly bonded to the -SO2- group explicitly stated in the formula in the alkyl group; and in the case of formula (BX-6), it is equivalent to a carbon atom directly bonded to the N- group explicitly stated in the formula in the alkyl group) has a substituent, it is also preferred to be a substituent other than a fluorine atom or a cyano group.

[0687] Furthermore, the carbon atoms of the aforementioned alkyl groups can be replaced by carbonyl carbons.

[0688] The aryl group is preferably phenyl or naphthyl, and more preferably phenyl.

[0689] 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.

[0690] In formula (Ia-1), there are no particular limitations on the divalent linking group represented by L1, and examples include -CO-, -NR-, -CO-, -O-, -S-, -SO-, -SO2-, 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), and divalent aliphatic heterocyclic groups (preferably having at least one N atom, O atom, ...). 5-10 membered rings (preferably 5-7 membered rings, more preferably 5-6 membered rings) containing S or Se atoms, divalent aromatic heterocyclic groups (preferably 5-10 membered rings, more preferably 5-7 membered rings, more preferably 5-6 membered rings having at least one N, O, S, or Se atom within the ring structure), divalent aromatic hydrocarbon cyclic groups (preferably 6-10 membered rings, more preferably 6 membered rings), and divalent linking groups formed by combining a plurality of these. Examples of R include hydrogen atoms or monovalent organogroups. There are no particular limitations on monovalent organogroups; for example, alkyl groups (preferably having 1-6 carbon atoms) are preferred.

[0691] Furthermore, 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).

[0692] Among them, the binary linking basis represented by L1 is preferably the binary linking basis represented by equation (L1).

[0693]

[0694] In equation (L1), L111 represents a single bond or a divalent linker.

[0695] There are no particular limitations on the divalent linker represented by L111. Examples include -CO-, -NH-, -O-, -SO-, -SO2-, or alkyl groups (preferably with 1 to 6 carbon atoms, which may be 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 may be included.

[0696] p represents an integer from 0 to 3, preferably an integer from 1 to 3.

[0697] v represents an integer of 0 or 1.

[0698] Xf1 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. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0699] Xf2 can independently represent 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.

[0700] Preferably, Xf1 and Xf2 are independently 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.

[0701] * indicates the location of the bond.

[0702] When L1 in equation (Ia-1) represents a divalent linker base represented by equation (L1), the bond (*) on the L111 side of equation (L1) is preferably an A12- bond with equation (Ia-1).

[0703] -Compounds represented by formulas (Ia-2)~(Ia-4)-

[0704] Next, the compounds represented by formulas (Ia-2) to (Ia-4) will be described.

[0705] [Chemical Formula 68]

[0706] 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 are no particular limitations on the monovalent anionic functional groups represented by A21a- and A21b-; for example, monovalent anionic groups selected from the group consisting of formulas (AX-1) to (AX-3) can be cited.

[0707] A22- represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A22- refers to a group containing the divalent anionic site A2- as described above. For example, divalent anionic functional groups represented by formulas (BX-8) to (BX-11) can be cited as examples of divalent anionic functional groups represented by A22-.

[0708]

[0709] M21a+, M21b+, and M22+ each independently represent an organic cation. As organic cations represented by M21a+, M21b+, and M22+, they are synonymous with M11+ mentioned above, and the preferred state is also the same.

[0710] L21 and L22 represent divalent organic groups independently.

[0711] Furthermore, in the above formula (Ia-2), in the compound PIa-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. Moreover, the acid dissociation constants a1-1 and a1-2 are equivalent to the aforementioned acid dissociation constant a1.

[0712] Furthermore, A21a- and A21b- can be the same or different from each other. Also, M21a+, M21b+, and M22+ can be the same or different from each other.

[0713] Furthermore, at least one of M21a+, M21b+, M22+, A21a-, A21b-, L21 and L22 may have an acid-decomposable group as a substituent.

[0714] 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 state is also the same.

[0715] The monovalent anionic functional group represented by A32- refers to a monovalent group containing the aforementioned anionic site A2-. There are no particular limitations on the monovalent anionic functional group represented by A32-; for example, monovalent anionic functional groups selected from the group consisting of the above formulas (BX-1) to (BX-7) can be cited.

[0716] A31b- represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A31b- refers to a group containing the divalent anionic site A1- as described above. For example, the divalent anionic functional group represented by formula (AX-4) shown below can be cited as an example of a divalent anionic functional group represented by A31b-.

[0717]

[0718] M31a+, M31b+, and M32+ each independently represent a monovalent organic cation. The organic cations represented by M31a+, M31b+, and M32+ are synonymous with M11+ mentioned above, and the preferred state is also the same.

[0719] L31 and L32 represent divalent organic groups independently.

[0720] Furthermore, in the above formula (Ia-3), in PIa-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. Moreover, the acid dissociation constants a1-3 and a1-4 are equivalent to the acid dissociation constant a1.

[0721] Furthermore, A31a- and A32- can be the same or different from each other. Also, M31a+, M31b+, and M32+ can be the same or different from each other.

[0722] Furthermore, at least one of M31a+, M31b+, M32+, A31a-, A32-, L31 and L32 may have an acid-decomposable group as a substituent.

[0723] In equation (Ia-4), A41a-, A41b-, and A42- independently represent monovalent anionic functional groups. Furthermore, the definitions of monovalent anionic functional groups represented by A41a- and A41b- are synonymous with A21a- and A21b- in equation (Ia-2) above. Also, the definition of a monovalent anionic functional group represented by A42- is synonymous with A32- in equation (Ia-3) above, and the preferred state is also the same.

[0724] M41a+, M41b+, and M42+ each independently represent an organic cation. The organic cations represented by M41a+, M41b+, and M42+ are synonymous with M11+ mentioned above, and the preferred state is also the same.

[0725] L41 represents a trivalent organic group.

[0726] Furthermore, in the above formula (Ia-4), in the compound PIa-4 formed by replacing the organic cations represented by M41a+, M41b+, and M42+ with H+, the acid dissociation constant a2 derived from the acidic site represented by A42H is greater than the acid dissociation constants a1-5 derived from the acidic site represented by A41aH and a1-6 derived from the acidic site represented by A41bH. Moreover, the acid dissociation constants a1-5 and a1-6 are equivalent to the aforementioned acid dissociation constant a1.

[0727] Furthermore, A41a-, A41b-, and A42- can be the same as or different from each other. Also, M41a+, M41b+, and M42+ can be the same as or different from each other.

[0728] Furthermore, at least one of M41a+, M41b+, M42+, A41a-, A41b-, A42- and L41 may have an acid-degradable group as a substituent.

[0729] There are no particular limitations on the divalent organogroups represented by L21 and L22 in formula (Ia-2) and L31 and L32 in formula (Ia-3). Examples include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkyl groups (preferably with 1 to 6 carbon atoms, which can be straight-chain or branched), cycloalkyl groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), and divalent aliphatic heterocyclic groups (preferably having at least one ring structure). 5-10 membered rings, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings, having at least one N, O, S, or Se atom in the ring structure; divalent aromatic heterocyclic groups (preferably 5-10 membered rings, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings); divalent aromatic hydrocarbon cyclic groups (preferably 6-10 membered rings, and even more preferably 6 membered rings); and divalent organogroups formed by combining a plurality of these. Examples of R above include hydrogen atoms or monovalent organogroups. There are no particular limitations on monovalent organogroups; for example, alkyl groups (preferably having 1-6 carbon atoms) are preferred.

[0730] Furthermore, 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).

[0731] The divalent organic groups represented by L21 and L22 in formula (Ia-2) and L31 and L32 in formula (Ia-3), for example, are also preferably divalent organic groups represented by the following formula (L2).

[0732]

[0733] In equation (L2), q represents an integer from 1 to 3. * indicates the bond position.

[0734] Xf represents either a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0735] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, it is even more preferred that Xf in both cases is a fluorine atom.

[0736] LA represents a single-bonded or divalent linker.

[0737] There are no particular limitations on the divalent linker represented by LA. Examples include -CO-, -O-, -SO-, -SO2-, alkyl groups (preferably with 1 to 6 carbons, and may 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.

[0738] Furthermore, the aforementioned alkyl groups, cycloalkyl groups, and divalent aromatic hydrocarbon cyclogroups may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0739] Examples of divalent organic groups represented by formula (L2) include *-CF2-*, *-CF2-CF2-*, *-CF2-CF2-CF2-*, *-Ph-O-SO2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, and *-Ph-OCO-CF2-*. Furthermore, *Ph* refers to an extensiphenyl group that may have substituents, preferably 1,4-extensiphenyl. There are no particular limitations on the substituents, but they are preferably alkyl (e.g., preferably with 1 to 10 carbon atoms, more preferably with 1 to 6 carbon atoms), alkoxy (e.g., preferably with 1 to 10 carbon atoms, more preferably with 1 to 6 carbon atoms), or alkoxycarbonyl (e.g., preferably with 2 to 10 carbon atoms, more preferably with 2 to 6 carbon atoms).

[0740] When L21 and L22 in formula (Ia-2) represent divalent organic groups represented by formula (L2), the bond (*) on the LA side of formula (L2) is preferably bonded to A21a- and A21b- in formula (Ia-2).

[0741] Furthermore, when L31 and L32 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 A31a- and A32- in formula (Ia-3).

[0742] -Compounds represented by formula (Ia-5)-

[0743] Next, equation (Ia-5) will be explained.

[0744]

[0745] 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-, but for example, monovalent anionic functional groups selected from the group consisting of formulas (AX-1) to (AX-3) can be cited.

[0746] A52a- and A52b- represent divalent anionic functional groups. Here, the divalent anionic functional groups represented by A52a- and A52b- refer to divalent groups containing the aforementioned anionic site A2-. 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 A22-.

[0747] M51a+, M51b+, M51c+, M52a+, and M52b+ each independently represent an organic cation. The organic cations represented by M51a+, M51b+, M51c+, M52a+, and M52b+ are synonymous with M11+ mentioned above, and the preferred state is also the same.

[0748] L51 and L53 independently represent divalent organic groups. As divalent organic groups represented by L51 and L53, they are synonymous with L21 and L22 in the above formula (Ia-2), and the preferred state is also the same.

[0749] L52 represents a trivalent organogroup. As a trivalent organogroup represented by L52, it is synonymous with L41 in the above formula (Ia-4), and the preferred state is also the same.

[0750] Furthermore, in the above formula (Ia-5), in the compound PIa-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. Moreover, 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.

[0751] Furthermore, A51a-, A51b-, and A51c- can be the same as or different from each other. Also, A52a- and A52b- can be the same as or different from each other. Also, M51a+, M51b+, M51c+, M52a+, and M52b+ can be the same as or different from each other.

[0752] Furthermore, at least one of M51b+, M51c+, M52a+, M52b+, A51a-, A51b-, A51c-, L51, L52 and L53 may have an acid-decomposable group as a substituent.

[0753] (Compound(2))

[0754] Compound (2) 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 containing 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.

[0755] Structural site Z: Nonionic site capable of neutralizing acids.

[0756] In compound (2), the definitions of structural site X and A1- and M1+ are the same as those in compound (1) above, and the preferred state is also the same.

[0757] In the above compound (2), in compound PII 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 of the acidic site represented by HA1, which is 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 PI.

[0758] Furthermore, for example, when compound (2) is a compound that produces an acid having two originating from the first acidic site X and the first acidic site Z, compound PII is equivalent to "a compound having two HA1s". Having determined the acid dissociation constant of compound PII, the acid dissociation constant when compound PII is "a compound having one A1- and one HA1" and the acid dissociation constant when "a compound having one A1- and one HA1" becomes "a compound having two A1-s", are equivalent to the acid dissociation constant a1.

[0759] The acid dissociation constant a1 is determined by the method described above for determining the acid dissociation constant.

[0760] The above compound PII is equivalent to the acid produced when compound (2) is irradiated by photochemical rays or radiation.

[0761] Furthermore, the two or more structural parts X mentioned above can be the same or different. Also, the two or more A1- and the two or more M1+ mentioned above can be the same or different.

[0762] There are no particular limitations on the nonionic site that can neutralize the acid in structural site Z. For example, it is preferred to be a site containing a group that can electrostatically interact with a proton or a functional group with electrons.

[0763] Examples of functional groups capable of electrostatic interaction with protons or possessing electrons include, for instance, cyclic polyethers and other functional groups with macrocyclic structures, or functional groups containing nitrogen atoms with non-shared electron pairs that do not contribute to π-conjugation. A nitrogen atom with a non-shared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure as shown in the following formula.

[0764]

[0765] 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.

[0766] There are no particular limitations on the compound (2), for example, compounds represented by the following formula (IIa-1) and the following formula (IIa-2) can be cited.

[0767]

[0768] In the above formula (IIa-1), A61a- and A61b- are synonyms of A11- in the above formula (Ia-1), and the preferred state is also the same. Also, M61a+ and M61b+ are synonyms of M11+ in the above formula (Ia-1), and the preferred state is also the same.

[0769] In the above formula (IIa-1), L61 and L62 are synonyms with L1 in the above formula (Ia-1), and the better state is also the same.

[0770] In formula (IIa-1), R2X represents a monovalent organogroup. There are no particular limitations on the monovalent organogroup represented by R2X. For example, -CH2- can be substituted by one or more combinations of alkyl groups (preferably with 1 to 10 carbon atoms, and can be straight-chain or branched), cycloalkyl groups (preferably with 3 to 15 carbon atoms), or alkenyl groups (preferably with 2 to 6 carbon atoms) selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-.

[0771] Furthermore, 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 cited.

[0772] Furthermore, in the above formula (IIa-1), in the compound PIIa-1 formed by replacing the organic cations represented by M61a+ and M61b+ with H+, the acid dissociation constants a1-7 and a1-8 derived from the acidic site represented by A61aH are equivalent to the above-mentioned acid dissociation constant a1.

[0773] Furthermore, in the aforementioned compound (IIa-1), the compound PIIa-1, formed by replacing the aforementioned cation sites M61a+ and M61b+ in the aforementioned structural site X with H+, is equivalent to HA61a-L61-N(R2X)-L62-A61bH. Also, compound PIIa-1 is the same acid as the acid produced by the compound represented by formula (IIa-1) through irradiation with photochemical rays or radiation.

[0774] Furthermore, at least one of M61a+, M61b+, A61a-, A61b-, L61, L62 and R2X may have an acid-degradable group as a substituent.

[0775] In equation (IIa-2) above, A71a-, A71b-, and A71c- are synonyms of A11- in equation (Ia-1) above, and the preferred state is also the same. Furthermore, M71a+, M71b+, and M71c+ are synonyms of M11+ in equation (Ia-1) above, and the preferred state is also the same.

[0776] In the above formula (IIa-2), L71, L72 and L73 are synonyms with L1 in the above formula (Ia-1), and the better state is also the same.

[0777] Furthermore, in the above formula (IIa-2), in the compound PIIa-2 formed by replacing the organic cations represented by M71a+, M71b+ and M71c+ with H+, the acid dissociation constants a1-9, a1-10, and a1-11 of the acidic site represented by A71aH are equivalent to the above-mentioned acid dissociation constant a1.

[0778] Furthermore, in the aforementioned compound (IIa-1), the compound PIIa-2, formed by replacing the aforementioned cation sites M71a+, M71b+, and M71c+ in the aforementioned structural site X with H+, is equivalent to HA71a-L71-N(L73-A71cH)-L72-A71bH. Also, compound PIIa-2 is the same acid as the acid produced by the compound represented by formula (IIa-2) through irradiation with photochemical rays or radiation.

[0779] Furthermore, at least one of M71a+, M71b-+, M71c+, A71a-, A71b-, A71c-, L71, L72 and L73 may have an acid-decomposable group as a substituent.

[0780] Examples of compounds (1) to (2) include sites other than cations.

[0781] [Chemical Formula 75]

[0782] [Chemical Formula 76]

[0783] The following are specific examples of photoacid generators, but are not limited to these.

[0784] [Chemical Formula 77]

[0785] [Chemical Formula 78]

[0786] [Chemical Formula 79]

[0787] When the composition of the present invention contains a photoacid generator (B), its content is not particularly limited. However, from the viewpoint that the cross-sectional shape of the formed pattern is more rectangular, it is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, relative to the total solid content of the composition. Furthermore, relative to the total solid content of the composition, 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.

[0788] Photoacid generator (B) can be used alone or in combination with two or more.

[0789] <Acid diffusion control agent>

[0790] The composition of the present invention may contain an acid diffusion control agent (C) that is not equivalent to the above-described compound (I).

[0791] The acid diffusion control agent acts as a quencher, which captures the acid generated by photoacid generators during exposure and inhibits the reaction of acid-decomposing resin in the unexposed area caused by excess generated acid.

[0792] There are no particular limitations on the types of acid diffusion control agents. 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.

[0793] Examples of compounds (CC) include onium salt compounds (CD) that are relatively weak acids relative to photoacid generators, and basic compounds (CE) whose basicity decreases or disappears upon exposure to photochemical rays or radiation.

[0794] Furthermore, for example, as a specific example of a basic compound (CA), the one described in paragraphs

[0132] to

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

[0137] to

[0155] of International Publication No. 2020 / 066824 can be cited; 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, the one described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824 can be cited; as a specific example of an onium salt compound having a nitrogen atom in the cation portion, the one described in paragraph

[0164] of International Publication No. 2020 / 066824 can be cited.

[0795] Furthermore, as a specific example of an onium salt compound (CD) that is a relatively weak acid relative to a photoacid generator, one can cite paragraphs

[0305] to

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

[0796] 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 can be used as acid diffusion control agents.

[0797] When the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent (or the total content if there are multiple agents) relative to the total solid content of the composition is preferably 0.1 to 15.0% by mass, more preferably 1.0 to 15.0% by mass.

[0798] In the composition of this invention, an acid diffusion control agent may be used alone or in combination with two or more.

[0799] <Hydrophobic resin>

[0800] The composition of the present invention may further contain a hydrophobic resin (D) that is different from resin (A).

[0801] Hydrophobic resins are preferably designed to exist on the surface of photoresist films, but unlike surfactants, their molecules do not necessarily have hydrophilic groups, and they can also help to uniformly mix polar and non-polar substances.

[0802] 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 degassing.

[0803] 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 chains of the resin; more preferably, it has two or more of these. Furthermore, 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 chains.

[0804] As a hydrophobic resin, the compounds described in paragraphs

[0275] to

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

[0805] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass relative to the total solid content of the composition, and more preferably 0.1 to 15.0% by mass.

[0806] <surfactants>

[0807] The composition of this invention may contain a surfactant (E). The presence of a surfactant enables the formation of patterns with superior adhesion and fewer development defects.

[0808] Fluorine-based and / or silicone-based surfactants are preferred.

[0809] As fluorine-based and / or silicon-based surfactants, examples include the surfactants disclosed in paragraphs

[0218] and

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

[0810] These surfactants can be used alone or in combination with more than one type.

[0811] When the composition of the present invention contains a surfactant, the content of the surfactant 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, relative to the total solid content of the photoresist composition.

[0812] Solvent

[0813] The composition of the present invention preferably contains a solvent (F).

[0814] The solvent preferably contains 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 also contain components other than (M1) and (M2).

[0815] The inventors have discovered that by using this solvent and the aforementioned resin in combination, the coatability of the photoresist composition can be improved while simultaneously forming patterns with fewer development defects. Although the reason is not yet clear, the inventors believe that this is because the solvent has a good balancing effect on the solubility, boiling point, and viscosity of the aforementioned resin, thus suppressing uneven film thickness and the formation of precipitates during spin coating.

[0816] 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.

[0817] When the solvent further contains components other than components (M1) and (M2), the content of components other than components (M1) and (M2) relative to the total amount of solvent is preferably 5 to 30% by mass.

[0818] The solvent content in the composition of the present invention is preferably set to a solid component concentration of 0.5-30% by mass, more preferably 1-20% by mass. This can further improve the coatability of the composition of the present invention.

[0819] Furthermore, the term "solid component" refers to all components other than the solvent, and as mentioned above, it refers to the components that form photosensitive or radiosensitive linear films.

[0820] The so-called solid component concentration refers to the mass percentage of the components other than the solvent relative to the total mass of the composition of this invention.

[0821] The term "total solids content" refers to the total mass of the components after removing the solvent from the entire composition of the present invention. Furthermore, the term "solids content," as described above, refers to the components after removing the solvent; for example, it can be a solid or a liquid at 25°C.

[0822] <Other Additives>

[0823] 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).

[0824] The composition of this invention may further contain a solubility-inhibiting compound. Here, "soil-inhibiting compound" refers to a compound with a molecular weight of 3000 or less that decomposes under the action of acid and has reduced solubility in organic developing solutions.

[0825] The composition of the present invention can be preferably used as a photosensitive composition for EUV light.

[0826] EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm). Therefore, fewer incident photons are emitted when exposed at the same sensitivity. Consequently, "photon shot noise," which probabilistically results in a higher 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 requires a trade-off with the requirement for high sensitivity.

[0827] [use]

[0828] The composition of this invention relates to a photosensitive or radiosensitive linear resin composition, which alters its properties upon irradiation with photosensitive rays or radiation. More specifically, the composition of this invention relates to a photosensitive or radiosensitive linear resin composition used in semiconductor manufacturing processes such as integrated circuits (ICs), in manufacturing circuit substrates such as liquid crystal or thermal heads, in fabricating mold structures for imprinting, in other photosensitive etching processes, or in manufacturing lithographic printing plates or acid-curable compositions. The patterns formed in this invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring processes, and MEMS (Micro Electro Mechanical Systems), etc.

[0829] Furthermore, the present invention also relates to the following compounds.

[0830] A compound represented by any one of the following general formulas (IA)-1 to (IA)-3.

[0831]

[0832] In general formulas (IA)-1 to (IA)-3, A11-, ~A13-, and ~A16- independently represent the acid anionic groups represented by formulas (A-1) or (A-2) below.

[0833] A12- represents an acidic anionic group represented by any one of the following formulas (B-1) to (B-3).

[0834] C11+~C16+ represent cationic groups independently.

[0835] L11 to L14 represent divalent organic groups independently.

[0836] L15 represents a trivalent organic group.

[0837]

[0838] In the above general formulas (A-1)~(A-2), RA represents an organic group.

[0839] * indicates the location of the bond.

[0840] [Chemical Formula 82]

[0841] In the above general formulas (B-1) to (B-3), * indicates the bond position.

[0842] In formulas (IA)-1 to (IA)-3, C11+ to C16+, L11 to L14 and L15 are respectively synonyms with C11+ to C16+, L11 to L14 and L15 in the above general formulas (I)-1 to (I)-3 in the composition of the present invention.

[0843] In formula (A-2), RA is synonymous with RA in the above formula (A-2) of the composition of the present invention.

[0844] <Methods for forming photosensitive or radiosensitive linear films and patterns>

[0845] There are no particular limitations on the steps of the pattern forming method using the above-mentioned components, but it is preferred to have the following process.

[0846] Process 1: A process for forming a photosensitive or radiosensitive linear film on a substrate using a photosensitive radioactive or radiosensitive linear resin composition.

[0847] Process 2: The process of exposing photosensitive or radiosensitive linear films.

[0848] Process 3: The process of developing exposed photosensitive or radiosensitive linear films using a developing solution.

[0849] The steps of each of the above processes will be described in detail below.

[0850] (Process 1: Photosensitive or radiosensitive linear film formation process)

[0851] Process 1 is a process of forming a photosensitive radioactive or radiosensitive linear film on a substrate using the components of the present invention.

[0852] As a method for forming a photosensitive radioactive or radioactive linear film on a substrate by means of a photosensitive radioactive or radioactive linear resin composition, for example, a method of coating a photosensitive radioactive or radioactive linear resin composition onto a substrate can be cited.

[0853] Furthermore, it is preferable to filter the photosensitive or radiosensitive linear resin composition as needed before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. Also, the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0854] Photosensitive or radiosensitive linear resin compositions can be applied to substrates used for manufacturing integrated circuit devices (e.g., silicon- or silicon dioxide-coated substrates) using appropriate coating methods such as spin coaters or coating machines. Spin coating using a spin coater is preferred. The rotation speed when using a spin coater is preferably 1000–3000 rpm.

[0855] After coating the substrate with a photosensitive or radiosensitive linear resin composition, the substrate can be dried to form a photoresist film. Furthermore, depending on the requirements, various substrate films (inorganic films, organic films, antireflective films) can be formed on the underside of the photoresist film.

[0856] 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.

[0857] There is no particular limitation on the thickness of the photosensitive or radiosensitive linear film (typically a photoresist film), but from the viewpoint of being able to form finer patterns with higher precision, 10 to 120 nm is preferred.

[0858] In the case of EUV exposure, the film thickness of the photosensitive radioactive or radiosensitive linear film is preferably 10-65 nm, and more preferably 15-50 nm. Furthermore, in the case of ArF immersion exposure, the film thickness of the photosensitive radioactive or radiosensitive linear film is preferably 10-120 nm, and more preferably 15-90 nm.

[0859] In addition, a topcoat composition can be used to form a topcoat on the upper layer of a photosensitive radioactive or radiosensitive linear film.

[0860] The composition of the top coating is preferably not mixed with the photosensitive radioactive or radioactive linear film and can be uniformly coated on the upper layer of the photosensitive radioactive or radioactive linear 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.

[0861] For example, it is preferable to form a top coating containing an alkaline compound as described in Japanese Patent Application Publication No. 2013-61648 on a photosensitive or radiosensitive linear film. Specific examples of alkaline compounds that can be contained in the top coating include alkaline compounds that can contain a composition of a photosensitive or radiosensitive linear resin.

[0862] Furthermore, the top coating is preferably a compound containing at least one group or bond selected from the group consisting of ether bonds, thioether bonds, hydroxyl groups, thiols, carbonyl bonds and ester bonds.

[0863] (Process 2: Exposure Process)

[0864] Process 2 is a process for exposing photosensitive radioactive or radiosensitive linear films.

[0865] As an exposure method, one example is the method of irradiating the formed photosensitive or radiosensitive linear film with photochemical rays or radiation through a prescribed mask.

[0866] 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 nm), X-rays, and electron beams.

[0867] After exposure, it is best to bake (heat) the exposed area before development. Baking promotes the reaction of the exposed area, thereby improving sensitivity and pattern shape.

[0868] The preferred heating temperature is 80~150℃, more preferably 80~140℃, and even more preferably 80~130℃.

[0869] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.

[0870] 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.

[0871] This process is also known as post-exposure baking.

[0872] (Process 3: Development Process)

[0873] Process 3 is a process that uses a developer to develop and pattern the exposed photosensitive or radiosensitive linear film.

[0874] The developer can be an alkaline developer or a developer containing organic solvents (hereinafter also referred to as an organic developer).

[0875] 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 the developer to accumulate on the substrate surface and remain still 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).

[0876] 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.

[0877] 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 even more preferably 20 to 120 seconds.

[0878] The optimal temperature for the developer is 0~50℃, and more preferably 15~35℃.

[0879] Alkaline developer is preferably an alkaline aqueous solution containing 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 0.1% to 20% by mass. Furthermore, the pH value of the alkaline developer is typically 10.0 to 15.0.

[0880] 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.

[0881] 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.

[0882] 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.

[0883] (Other processes)

[0884] The above-mentioned pattern formation method preferably includes a rinsing process after process 3.

[0885] 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.

[0886] An appropriate amount of surfactant can also be added to the rinsing solution.

[0887] 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. A solution containing a common organic solvent can be used. Preferably, the rinsing solution is a rinsing solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0888] 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).

[0889] Furthermore, the pattern forming method of the present invention may include a post-bake process after the washing process. Through this process, the developer and washing solution remaining between and inside the pattern are removed by baking. Furthermore, this process also has the effect of smoothing the photoresist pattern and improving the surface roughness of the pattern. The post-washing process is typically performed at 40~250°C (preferably 90~200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0890] 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) to form a pattern on the substrate.

[0891] 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.

[0892] 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 content of impurities in these materials is preferably less than 1 ppm by mass, more preferably less than 10 ppb by mass, further preferably less than 100 ppt by mass, particularly preferably less than 10 ppt by mass, and most 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. 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.

[0893] 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.

[0894] Furthermore, as methods to reduce impurities such as metals contained in various materials, examples include selecting raw materials with low metal content as the raw materials for various materials, filtering the raw materials for various materials using filters, and using Teflon (registered trademark) to form a lining in the device to carry out distillation under conditions that suppress contamination as much as possible.

[0895] 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 metal and other impurities 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 below 100 parts per trillion (ppt), more preferably below 10 ppt, and even more preferably below 1 ppt. There is no particular limitation on the lower limit, but it is preferably above 0 ppt.

[0896] 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 electrostatic charging 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.

[0897] For example, SUS (stainless steel) or various pipes coated with antistatic-treated polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can be used for pharmaceutical piping. Similarly, antistatic-treated polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can also be used for filters and O-rings.

[0898] <Manufacturing Methods of Electronic Components>

[0899] Furthermore, the present invention also relates to a method for manufacturing an electronic component incorporating the above-described pattern forming method, and an electronic component manufactured by the method.

[0900] As a preferred embodiment of the electronic component of the present invention, it can be exemplified by being mounted on electrical and electronic machines (home appliances, OA (Office Automation), media-related machines, optical machines, and communication machines, etc.).

[0901] [Example]

[0902] The present invention will now be described in more detail based on embodiments. The materials, amounts, ratios, processing contents, and processing steps shown in the following embodiments may 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.

[0903] <Resin (A)>

[0904] The following shows the structure of the repeating units of the resin (A) used, as well as their composition ratio (moles%), weight average molecular weight (Mw), and dispersion (Mw / Mn).

[0905] The composition ratio (moles %; corresponding from left to right), weight average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit in the resin (A) used are also shown.

[0906] In addition, the weight-average molecular weight (Mw) and dispersibility (Mw / Mn) of resin (A) were determined by GPC (solvent: tetrahydrofuran (THF)). Furthermore, the composition ratio (moles%) of the resin was determined by 13C-NMR (Nuclear Magnetic Resonance).

[0907] [Chemical Formula 83]

[0908] <Compound (I)>

[0909] (Synthetic Example 1) Synthesis of Compound X-1

[0910]

[0911] 10.0 g (22.9 mmol) of compound (X-1-A), 100 mL of acetonitrile, and 5.9 g (45.7 mmol) of diisopropylethylamine were added to a 300 mL three-necked flask and cooled to 0 °C. Then, 8.7 g (22.9 mmol) of compound (X-1-B) was slowly added, and the reaction was allowed to proceed for 2 hours. After adding 200 mL of dichloromethane and 100 mL of water and removing the aqueous layer, the organic layer was washed twice with 100 mL of water, and the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column chromatography (dissolving in a chloroform / methanol mixture) to give 11.6 g (70%) of compound (X-1) as a white solid.

[0912] ¹H-NMR (300MHz, dimethyl sulfoxide): δ (ppm) 7.81 (m, 29H)

[0913] 19F-NMR (300MHz, dimethyl monoxide): -109.03 (2F)

[0914] (Synthetic Example 2) Synthesis of Compound X-8

[0915]

[0916] 10.0 g (17.4 mmol) of compound (X-8-A), 100 mL of acetonitrile, and 4.5 g (34.9 mmol) of diisopropylethylamine were added to a 300 mL three-necked flask and cooled to 0 °C. Then, 6.6 g (22.9 mmol) of compound (X-8-B) was slowly added, and the reaction was allowed to proceed for 2 hours. After adding 200 mL of dichloromethane and 100 mL of water and removing the aqueous layer, the organic layer was washed twice with 100 mL of water, and the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column chromatography (dissolving in a chloroform / methanol mixture) to give 10.4 g (68%) of compound (X-8) as a white solid.

[0917] ¹H-NMR (300MHz, dimethyl sulfoxide): δ (ppm) 6.81 (d, ¹H), 7.66 (m, 4H), 7.83 (m, ¹⁶H), 8.29 (m, ³H)

[0918] 19F-NMR (300MHz, dimethyl sulfoxide): -118.69 (2F), -114.11 (2F), -113.13 (2F)

[0919] Compounds (X-2) to (X-7) and compounds (X-9) to (X-16) were synthesized in the same manner as in Synthesis Examples 1 and 2 described above. The structures of compounds (X-1) to (X-16) are shown below.

[0920]

[0921] [Chemical Formula 87]

[0922] (acid dissociation constant pKa of the acid produced by compound (I))

[0923] Table 1 shows the acid dissociation constant pKa of the acid produced by compound (I).

[0924] Furthermore, when determining the acid dissociation constant pKa of the acid produced by compound (I), specifically, compounds formed by substituting the acid anionic groups in compounds X-1 to X-16 with acid groups were used as the target. As described above, the values ​​were obtained by calculation using software package 1 from ACD / Labs, based on a database of Hammett substituent constants and known literature values. Also, when pKa could not be calculated using the above method, the value obtained using Gaussian 16 based on DFT (density functional theory) was used.

[0925] In the table below, "pKa1" represents the acid dissociation constant in the first stage, "pKa2" represents the acid dissociation constant in the second stage, and "pKa3" represents the acid dissociation constant in the third stage. The smaller the pKa value, the higher the acidity.

[0926] As described above, compounds X-1 to X-3, X-5 to X-8, and X-10 to X-14 are equivalent to the aforementioned compound (I). Here, pKa1 is equivalent to the aforementioned acid dissociation constant a1, and pKa2 is equivalent to the aforementioned acid dissociation constant a2.

[0927] Furthermore, as mentioned above, compound X-4 is also equivalent to compound (I) described above. Here, pKa1 is equivalent to the acid dissociation constant a1 described above, pKa2 is equivalent to the acid dissociation constant a2 described above, and pKa3 is equivalent to the acid dissociation constant a3 described above.

[0928] The acid produced by compound X-4 (a compound formed by replacing two strontium cations of compound X-4 with H+ and adding H+ to a SO3-) has a symmetrical structure, so the acid dissociation constant pKa of the acid groups derived from the three acid anionic groups is theoretically the same.

[0929] For convenience, they are recorded as "pKa1", "pKa2" and "pKa3" respectively.

[0930] Furthermore, as mentioned above, compounds X-9, X-15, and X-16 are also equivalent to the aforementioned compound (I). Here, pKa1 is equivalent to the aforementioned acid dissociation constant a1, and pKa2 is equivalent to the aforementioned acid dissociation constant a2.

[0931] In each compound, the acid dissociation constant pKa of the acid group derived from the two acid anionic groups is theoretically the same.

[0932] For convenience, they are recorded as "pKa1" and "pKa2" respectively.

[0933] [Table 1]

[0934] Furthermore, in Table 1, the number of linking ions indicates the number of cationic and anionic groups in the chain containing zwitterionic groups in compound (I).

[0935] <Photoacid Generator (B)>

[0936] The following shows the structure of a photoacid generator that is not equivalent to the compound (I) used.

[0937]

[0938] <Acid diffusion control agent>

[0939] The following shows the structure of an acid diffusion control agent that is not equivalent to the compound (I) used.

[0940] [Chemical Formula 89]

[0941] <Hydrophobic resin>

[0942] The following shows the structure of the repeating units of the hydrophobic resin used, as well as their composition ratio (moles%), weight average molecular weight (Mw), and dispersion (Mw / Mn).

[0943] The composition ratio (moles %; corresponding from left to right), weight average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit in the hydrophobic resin used are also shown.

[0944] In addition, the weight-average molecular weight (Mw) and dispersibility (Mw / Mn) of resin (A) were determined by GPC (solvent: tetrahydrofuran (THF)). Furthermore, the composition ratio (moles%) of the resin was determined by 13C-NMR (Nuclear Magnetic Resonance).

[0945]

[0946] <surfactants>

[0947] E-1 was used as a surfactant.

[0948] E-1: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorinated surfactant)

[0949] Solvent

[0950] The solvents used are shown below.

[0951] F-1: Propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane)

[0952] F-2: Propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol)

[0953] F-3: Cyclohexanone

[0954] F-4: γ-Butyrolactone

[0955] F-5: Ethyl lactate

[0956] (Examples 1-1~1-21, 2-1~2-21, 3-1~3-14, 4-1~4-14, Comparative Examples 1-1~1-3, 2-1~2-3, 3-1~3-3, 4-1~4-3)

[0957] <Preparation of Photoresist Compositions> (ArF Exposure)

[0958] (Examples 1-1 to 1-21, 2-1 to 2-21, Comparative Examples 1-1 to 1-3, 2-1 to 2-3)

[0959] The components shown in Table 2 were dissolved in the solvents shown in Table 2 to prepare a solution with a solid component concentration of 4.0% by mass, and then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare the photoresist composition.

[0960] Furthermore, the term "solid component" refers to all components other than the solvent. The obtained photoresist composition was used in the examples and comparative examples.

[0961] Furthermore, the "mass%" column in the table shows the content (mass%) of each component relative to the total solid content in the photoresist composition. Also, the table records the amount (parts by mass) of the solvent used.

[0962] <Pattern Formation Method (1): ArF Exposure, Alkaline Development (Positive Pattern)>

[0963] Using a Tokyo Electron Mark 8 spin coater, the newly manufactured photoresist composition shown in Table 2 was coated onto a 6-inch Si wafer pretreated with hexamethyldisilazane (HMDS), and dried on a hot plate at 100°C for 60 seconds to obtain a photoresist film with a thickness of 90 nm. Here, 1 inch is 0.0254 μm.

[0964] The wafer with the photoresist film was patterned using an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193nm, NA 0.50) via an exposure mask. Then, after baking at 115°C for 60 seconds, it was developed with a 2.38% (w / w) tetramethylammonium hydroxide aqueous solution (TMAHaq) for 30 seconds, rinsed with pure water, and then spin-dried. This yielded a 1:1 line and space pattern photoresist pattern with a linewidth of 50nm.

[0965] <Performance Evaluation>

[0966] [Residue]

[0967] The cross-section of a 1:1 line and gap pattern with a linewidth of 50 nm was observed using a scanning electron microscope (SEM (Hitachi, Ltd. S-9380II) and the presence or absence of residue was evaluated using two levels, A and B.

[0968] A: When no scum can be visually observed

[0969] B: When scum is observed visually

[0970] [Maintain stability]

[0971] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The exposure amount used to resolve a photoresist pattern with a linewidth of 50 nm and a 1:1 line and gap was set as the sensitivity (Eop).

[0972] After storing the photoresist composition at room temperature (23°C) for one month, a 1:1 line and gap pattern with a linewidth of 50 nm was formed following the same procedure as described above. The exposure amount when resolving this photoresist pattern was defined as the sensitivity (Eop). The sensitivity difference between using the freshly manufactured composition and using the composition stored at room temperature for one month after manufacturing was evaluated according to the following criteria: {|(exposure amount when resolving the pattern using the composition stored at room temperature for one month - exposure amount when resolving the pattern using the freshly manufactured composition)|}.

[0973] A: Sensitivity difference is less than 1 mJ / cm2.

[0974] B: Sensitivity difference is greater than 1 mJ / cm2 and less than 3 mJ / cm2.

[0975] C: Sensitivity difference is above 3 mJ / cm2.

[0976] [Pattern Shape]

[0977] The cross-section of a 1:1 line and gap pattern with a linewidth of 50 nm was observed using a scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)). The linewidth Lb at the bottom of the photoresist pattern and the linewidth La at the top of the photoresist pattern were measured. The pattern shape was evaluated using four grades: A, B, C, and D.

[0978] A: (Lb / La)≦1.03

[0979] B: 1.03 < (Lb / La) ≦ 1.06

[0980] C: 1.06 < (Lb / La) ≦ 1.1

[0981] D: 1.1 < (Lb / La)

[0982] <Pattern Formation Method (2): ArF Exposure, Alkaline Development (Negative)>

[0983] Using a spin coater "Mark8" manufactured by Tokyo Electron, the photoresist composition shown in Table 2 was coated onto a 6-inch Si wafer pre-treated with hexamethyldisilazane (HMDS), and dried on a hot plate at 100°C for 60 seconds to obtain a photoresist film with a thickness of 90 nm. Here, 1 inch is 0.0254 μm.

[0984] The wafer with the photoresist film was patterned using an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193nm, NA 0.50) via an exposure mask. Then, it was baked at 115°C for 60 seconds, developed with n-butyl acetate for 30 seconds, and then spin-dried. This yielded a 1:1 line and gap pattern of photoresist with a linewidth of 50nm.

[0985] <Performance Evaluation>

[0986] [Residue]

[0987] The cross-section of a 1:1 line and gap pattern with a linewidth of 50 nm was observed using a scanning electron microscope (SEM (Hitachi, Ltd. S-9380II) and the presence or absence of residue was evaluated using two levels, A and B.

[0988] A: When no scum can be visually observed

[0989] B: When scum is observed visually

[0990] [Maintain stability]

[0991] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The exposure amount used to resolve a photoresist pattern with a linewidth of 50 nm and a 1:1 line and gap was set as the sensitivity (Eop).

[0992] After storing the photoresist composition at room temperature (23°C) for one month, a 1:1 line and gap pattern with a linewidth of 50 nm was formed following the same procedure as described above. The exposure amount when resolving this photoresist pattern was defined as the sensitivity (Eop). The sensitivity difference between using the freshly manufactured composition and using the composition stored at room temperature for one month after manufacturing was evaluated according to the following criteria: {|(exposure amount when resolving the pattern using the composition stored at room temperature for one month - exposure amount when resolving the pattern using the freshly manufactured composition)|}.

[0993] A: Sensitivity variation less than 1 mJ / cm2.

[0994] B: Sensitivity difference is greater than 1 mJ / cm2 and less than 3 mJ / cm2.

[0995] C: Sensitivity difference is above 3 mJ / cm2.

[0996] [Pattern Shape]

[0997] The cross-section of a 1:1 line and gap pattern with a linewidth of 50 nm was observed using a scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)). The linewidth Lb at the bottom of the photoresist pattern and the linewidth La at the top of the photoresist pattern were measured. The pattern shape was evaluated using four grades: A, B, C, and D.

[0998] A: (Lb / La)≦1.03

[0999] B: 1.03 < (Lb / La) ≦ 1.06

[1000] C: 1.06 < (Lb / La) ≦ 1.1

[1001] D: 1.1 < (Lb / La)

[1002] <Preparation of Photoresist Compositions> (EUV Exposure)

[1003] (Examples 3-1 to 3-14, 4-1 to 4-14, Comparative Examples 3-1 to 3-3, 4-1 to 4-4)

[1004] The components shown in Table 3 were dissolved in the solvents shown in Table 3 to prepare a solution with a solid component concentration of 2.0% by mass, and then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare the photoresist composition.

[1005] Furthermore, the term "solid component" refers to all components other than the solvent. The obtained photoresist composition was used in the examples and comparative examples.

[1006] Furthermore, the "mass%" column in the table shows the content (mass%) of each component relative to the total solid content in the photoresist composition. Also, the table records the amount (parts by mass) of the solvent used.

[1007] <Pattern Formation Method (3): EUV Exposure, Alkaline Development (Positive Type)>

[1008] The substrate 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 substrate film with a thickness of 20 nm. The photoresist composition shown in Table 3 was then coated onto it and baked at 100°C for 60 seconds to form a photoresist film with a thickness of 30 nm.

[1009] The silicon wafer with the obtained photoresist film was patterned using an EUV exposure apparatus (Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, Exitech). Furthermore, a mask with a line size of 50 nm and a line-to-gap ratio of 1:1 was used as a reticle.

[1010] After exposure, the photoresist film was baked at 90°C for 60 seconds, then developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, followed by rinsing with pure water for 30 seconds. It was then rotated and dried to obtain a 1:1 line and gap pattern of photoresist with a linewidth of 50 nm.

[1011] <Performance Evaluation>

[1012] [Residue]

[1013] The cross-section of a 1:1 line and gap pattern with a linewidth of 50 nm was observed using a scanning electron microscope (SEM (Hitachi, Ltd. S-9380II) and the presence or absence of residue was evaluated using two levels, A and B.

[1014] A: When no scum can be visually observed

[1015] B: When scum is observed visually

[1016] [Maintain stability]

[1017] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The exposure amount used to resolve a photoresist pattern with a linewidth of 50 nm and a 1:1 line and gap was set as the sensitivity (Eop).

[1018] After storing the photoresist composition at room temperature (23°C) for one month, a 1:1 line and gap pattern with a linewidth of 50 nm was formed following the same procedure as described above. The exposure amount when resolving this photoresist pattern was defined as the sensitivity (Eop). The sensitivity difference between using the freshly manufactured composition and using the composition stored at room temperature for one month after manufacturing was evaluated according to the following criteria: {|(exposure amount when resolving the pattern using the composition stored at room temperature for one month - exposure amount when resolving the pattern using the freshly manufactured composition)|}.

[1019] A: Sensitivity difference is less than 1 mJ / cm2.

[1020] B: Sensitivity difference is greater than 1 mJ / cm2 and less than 3 mJ / cm2.

[1021] C: Sensitivity difference is above 3 mJ / cm2.

[1022] [Pattern Shape]

[1023] The cross-section of a 1:1 line and gap pattern with a linewidth of 50 nm was observed using a scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)). The linewidth Lb at the bottom of the photoresist pattern and the linewidth La at the top of the photoresist pattern were measured. The pattern shape was evaluated using four grades: A, B, C, and D.

[1024] A: (Lb / La)≦1.03

[1025] B: 1.03 < (Lb / La) ≦ 1.06

[1026] C: 1.06 < (Lb / La) ≦ 1.1

[1027] D: 1.1 < (Lb / La)

[1028] <Pattern Formation Method (4): EUV Exposure, Organic Solvent Development (Negative Type)>

[1029] 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 3 was then coated onto it and baked at 100°C for 60 seconds to form a photoresist film with a thickness of 30 nm.

[1030] The silicon wafer with the obtained photoresist film was patterned using an EUV exposure apparatus (Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, Exitech). Furthermore, a mask with a line size of 50 nm and a line-to-gap ratio of 1:1 was used as a reticle.

[1031] 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 1:1 line and gap pattern of photoresist with a linewidth of 50 nm.

[1032] <Performance Evaluation>

[1033] [Residue]

[1034] The cross-section of a 1:1 line and gap pattern with a linewidth of 50 nm was observed using a scanning electron microscope (SEM (Hitachi, Ltd. S-9380II) and the presence or absence of residue was evaluated using two levels, A and B.

[1035] A: When no scum can be visually observed

[1036] B: When scum is observed visually

[1037] [Maintain stability]

[1038] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The exposure amount used to resolve a photoresist pattern with a linewidth of 50 nm and a 1:1 line and gap was set as the sensitivity (Eop).

[1039] After storing the photoresist composition at room temperature (23°C) for one month, a 1:1 line and gap pattern with a linewidth of 50 nm was formed following the same procedure as described above. The exposure amount when resolving this photoresist pattern was defined as the sensitivity (Eop). The sensitivity difference between using the freshly manufactured composition and using the composition stored at room temperature for one month after manufacturing was evaluated according to the following criteria: {|(exposure amount when resolving the pattern using the composition stored at room temperature for one month - exposure amount when resolving the pattern using the freshly manufactured composition)|}.

[1040] A: Sensitivity difference is less than 1 mJ / cm2.

[1041] B: Sensitivity difference is greater than 1 mJ / cm2 and less than 3 mJ / cm2.

[1042] C: Sensitivity difference is above 3 mJ / cm2.

[1043] [Pattern Shape]

[1044] The cross-section of a 1:1 line and gap pattern with a linewidth of 50 nm was observed using a scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)). The linewidth Lb at the bottom of the photoresist pattern and the linewidth La at the top of the photoresist pattern were measured. The pattern shape was evaluated using four grades: A, B, C, and D.

[1045] A: (Lb / La)≦1.03

[1046] B: 1.03 < (Lb / La) ≦ 1.06

[1047] C: 1.06 < (Lb / La) ≦ 1.1

[1048] D: 1.1 < (Lb / La)

[1049] The evaluation results are shown in Tables 2 and 3.

[1050]

[1051]

[1052]

[1053] [Table 5]

[1054] As shown in Tables 2-3 above, the photoresist composition of the present invention has been confirmed to have excellent storage stability, and when fine patterns are formed by alkaline development or organic solvent development, excellent pattern shapes can be obtained while greatly reducing the generation of residues. On the other hand, these properties are insufficient in the photoresist composition of the comparative examples.

[1055] [Industrial Applicability]

[1056] According to the present invention, a photosensitive radioactive or radioactive linear resin composition is provided, which exhibits excellent storage stability and, when forming fine patterns (especially with linewidth or gap width of 50 nm or less), achieves excellent pattern shape while significantly reducing residue generation. Furthermore, according to the present invention, a photosensitive radioactive or radioactive linear film using the above-described photosensitive radioactive or radioactive linear resin composition, a pattern forming method, a method for manufacturing electronic components, and a compound are provided.

[1057] Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

[1058] This application is based on Japanese Patent Application No. 2021-124857, filed on July 29, 2021, the contents of which are incorporated herein by reference.

Claims

1. A photosensitive or radiosensitive linear resin composition, comprising a compound (I) having an ionic and zwitterionic structure that produces an acid upon irradiation by photosensitive rays or radiation, wherein, The compound (I) is a compound represented by any one of the following general formulas (I)-1 to (I)-3, in which A11- to A16- independently represent acidic anionic groups, C11+ to C16+ independently represent cationic groups, L11 to L14 independently represent divalent organic groups, and L15 represents trivalent organic groups. In compound PI-1, which is a compound represented by general formula (I)-1, wherein the counter cation of the acidic anionic group represented by A11- is replaced with H+ and H+ is added to the acidic anionic group represented by A12-, the pKa of the group represented by A11H is lower than the pKa of the group represented by A12H. In compound PI-2, which is a compound represented by general formula (I)-2, wherein the counter cation of the acid anionic group represented by A13- is replaced with H+ and H+ is added to the acid anionic group represented by A14-, the pKa of the group represented by A13H is lower than the pKa of the group represented by A14H. In compound PI-3, which is a compound represented by general formula (I)-3, wherein H+ is added to the acid anionic group represented by A15- and the counter cation of the acid anionic group represented by A16- is replaced with H+, the pKa of the group represented by A15H is lower than the pKa of the group represented by A16H.

2. The photosensitive radioactive or radiosensitive linear resin composition as described in claim 1, wherein, The compound (I) is a compound in which one or more cationic groups and two or more anionic groups are covalently linked.

3. A photosensitive radioactive or radiosensitive linear resin composition as described in claim 1 or 2, wherein, The compound (I) is a compound consisting of one cationic group and two anionic groups linked by covalent bonds.

4. A photosensitive radioactive or radiosensitive linear resin composition as described in claim 1 or 2, wherein, The ionic structure and the zwitterionic structure are each structures containing acid anionic groups, and the compound (I) generates multiple acid groups with different pKa by irradiation with photochemical rays or radiation.

5. A photosensitive radioactive or radiosensitive linear resin composition as described in claim 1 or 2, wherein, In the general formulas (I)-1 to (I)-3, A11-, A13- to A16- respectively independently represent the acid anionic groups represented by the following formulas (A-1) or (A-2), where RA represents an organic group and * represents a bond position.

6. A photosensitive radioactive or radiosensitive linear resin composition as described in claim 1 or 2, wherein, In the general formula (I)-1, A12- represents an acidic anionic group represented by any one of the following formulas (B-1) to (B-3), where * indicates the bond position.

7. A photosensitive radioactive or radiosensitive linear film formed from a photosensitive radioactive or radiosensitive linear resin composition as described in any one of claims 1 to 6.

8. A pattern forming method comprising the following processes: a process of forming a photosensitive radioactive or radioactive linear resin composition on a substrate from any one of claims 1 to 6; a process of exposing the photosensitive radioactive or radioactive linear film; and a process of developing the exposed photosensitive radioactive or radioactive linear film using a developing solution.

9. A method for manufacturing an electronic component, comprising the pattern forming method as described in claim 8.

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