Pattern forming method, radiation-sensitive or radio-sensitive resin composition, and method for manufacturing electronic device

Abstract

The present application provides a pattern forming method, a radiation-sensitive or radio-sensitive resin composition, and a manufacturing method of an electronic device including the pattern forming method, the pattern forming method including: a step of forming a film using a radiation-sensitive or radio-sensitive resin composition containing a resin (A) whose polarity increases by the action of an acid, a photo-acid generator, an acid diffusion control agent, and a solvent, and at least one of the photo-acid generator and the acid diffusion control agent including a sulfonium cation and an anion having an iodine atom; a step of exposing the film; and a step of developing the exposed film using an organic treatment liquid containing butyl acetate and a hydrocarbon having 9 or more and 12 or less carbon atoms.

Description

Technical Field

[0001] This invention relates to a pattern forming method, a photosensitive radioactive or radioactive linear resin composition, and a method for manufacturing electronic devices. More specifically, this invention relates to an ultra-micro lithography process preferably applicable to manufacturing processes of ultra-large-scale integrated circuits (LSI) and high-capacity microchips, nanoimprint stencil fabrication processes, and high-density information recording media; and to other lithography processes, a photosensitive radioactive or radioactive linear resin composition, a pattern forming method, and a method for manufacturing electronic devices. Background Technology

[0002] Previously, in the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrations), microfabrication based on photolithography using resist compositions was performed. 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. Along with this, the exposure wavelength has also trended towards shorter wavelengths, from gamma rays to i-rays, and further to KrF excimer lasers. Currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as the light source have been developed. Furthermore, as a technique to further improve resolution, the so-called immersion method, which involves filling the space between the projection lens and the sample with a high-refractive-index liquid (hereinafter also referred to as "immersion liquid"), has been under development.

[0003] In addition to excimer lasers, photolithography technologies such as electron beam (EB), X-rays, and extreme ultraviolet (EUV) are also being developed and utilized. Along with this, resist compositions that effectively sense various photochemical rays or radiation have been developed.

[0004] Patent Document 1 describes a pattern forming method in which a film is formed using a photosensitive radioactive or radiosensitive linear resin composition, and after exposure, it is subjected to at least one of the following treatments: development and washing, using an organic processing solution containing butyl acetate and hydrocarbons having 11 or more carbon atoms.

[0005] Previous technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2022 / 158323 Summary of the Invention

[0008] The technical problem to be solved by the invention

[0009] Recently, the performance requirements for resist compositions and patterning methods have become increasingly stringent. In particular, there is a demand for improved line width roughness (LWR) and exposure latitude (EL) when forming fine patterns. LWR performance refers to the ability to reduce the LWR of the pattern.

[0010] Therefore, the objective of this invention is to provide a pattern forming method with excellent exposure latitude and LWR performance, and a photosensitive radioactive or radiosensitive linear resin composition. Furthermore, another objective of this invention is to provide a method for manufacturing an electronic device including the above-described pattern forming method.

[0011] means for solving technical problems

[0012] The inventors have discovered that the above-mentioned problems can be solved by the following structure. [1]

[0014] A method for forming a pattern, comprising:

[0015] (1) A step of forming a film using a photosensitive radioactive or radioactive linear resin composition, wherein the photosensitive radioactive or radioactive linear resin composition contains a resin (A) whose polarity is increased by the action of an acid, a photoacid generator, an acid diffusion control agent, and a solvent, and at least one of the photoacid generator and the acid diffusion control agent contains a sulfonium cation and an anion having an iodine atom.

[0016] (2) The process of exposing the above-mentioned film; and

[0017] (3) The process of developing the above-exposed film using an organic treatment solution containing butyl acetate and hydrocarbons with 9 or more but less than 12 carbon atoms. [2]

[0019] According to the pattern forming method described in [1], the above-mentioned photoacid generator and the above-mentioned acid diffusion control agent contain sulfonium cations and monovalent anions having only one anionic site. [3]

[0021] According to the pattern forming method described in [1] or [2], the photoacid generator comprises at least one selected from the group consisting of -O-CO-, -O-CO-O- and -O-. [4]

[0023] The pattern forming method according to any one of [1] to [3], wherein the acid diffusion control agent comprises a carboxylate. [5]

[0025] The pattern forming method according to any one of [1] to [4], wherein the sulfonium cation has halogen atoms. [6]

[0027] The pattern forming method according to any one of [1] to [5], wherein the anion having iodine atoms has two or more iodine atoms. [7]

[0029] The pattern forming method according to any one of [1] to [6], wherein the resin (A) contains repeating units having iodine atoms. [8]

[0031] The pattern forming method according to any one of [1] to [7], wherein at least one of the above-mentioned photoacid generator and the above-mentioned acid diffusion control agent comprises a sulfonium cation having halogen atoms and an anion having two or more iodine atoms. [9]

[0033] A photosensitive or radiosensitive linear resin composition comprising a resin (A) whose polarity increases through the action of an acid, a photoacid generator, an acid diffusion control agent, and a solvent, wherein at least one of the photoacid generator and the acid diffusion control agent comprises a sulfonium cation and an anion having an iodine atom.

[0034] The above-mentioned photosensitive or radiosensitive linear resin composition is used to form patterns by developing with an organic processing liquid containing butyl acetate and hydrocarbons having 9 or more and 12 or fewer carbon atoms.

[10]

[0036] According to the photosensitive radioactive or radiosensitive linear resin composition described in [9], the photoacid generator and the acid diffusion control agent comprise sulfonium cations and monovalent anions having only one anionic site.

[11]

[0038] According to the photosensitive radioactive or radiosensitive linear resin composition of [9] or

[10] , wherein the photoacid generator comprises at least one selected from the group consisting of -O-CO-, -O-CO-O- and -O-.

[12]

[0040] The photosensitive or radiosensitive linear resin composition according to any one of [9] to

[11] , wherein the acid diffusion control agent comprises a carboxylate.

[13]

[0042] The photosensitive or radiosensitive linear resin composition according to any one of [9] to

[12] , wherein the sulfonium cation has halogen atoms.

[14]

[0044] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [9] to

[13] , wherein the anion having iodine atoms has two or more iodine atoms.

[15]

[0046] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [9] to

[14] , wherein the resin (A) comprises repeating units having iodine atoms.

[16]

[0048] A method for manufacturing an electronic device, comprising the pattern forming method described in any one of [1] to [8].

[0049] Invention Effects

[0050] According to the present invention, a pattern forming method with excellent exposure latitude and LWR performance, and a photosensitive radioactive or radiosensitive linear resin composition, are provided. Furthermore, according to the present invention, a method for manufacturing an electronic device including the above-described pattern forming method is provided. Detailed Implementation

[0051] The present invention will now be described in detail.

[0052] The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0053] In this specification, the terms "photochemical rays" or "radiation" refer to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet radiation represented by an excimer laser, extreme ultraviolet (EUV), X-rays, soft X-rays, and electron beams (EB).

[0054] In this specification, the term "light" refers to photochemical rays or radiation.

[0055] In this specification, the term "exposure" unless otherwise specified includes not only exposure using the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light, X-rays and EUV, but also depiction using particle beams such as electron beams and ion beams.

[0056] In this specification, the term "~" is used to mean that the values ​​recorded before and after it are included as lower and upper limits.

[0057] In this specification, (meth)acrylate means at least one of acrylate and methacrylate. Additionally, (meth)acrylic acid means at least one of acrylic acid and methacrylic acid.

[0058] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (also known as molecular weight distribution) (Mw / Mn) of the resin are defined as polystyrene equivalents obtained by GPC (Gel Permeation Chromatography) apparatus (Tosoh HLC-8120GPC) by GPC determination (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M, Tosoh, column temperature: 40 °C, flow rate: 1.0 mL / min, detector: Refractive Index Detector)).

[0059] Regarding the use of the term "group" (atomic group) in this specification, as long as it does not depart from the spirit of this invention, the description of "not substituted" and "not substituted" includes both groups without substituents and groups containing substituents. For example, the term "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group containing at least one carbon atom.

[0060] Unless otherwise specified, a monovalent substituent is preferred. Examples of substituents include monovalent nonmetallic groups other than hydrogen atoms, such as those selected from the following substituents T.

[0061] (Substituent T)

[0062] Examples of substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; cycloalkoxy groups; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; aryloxycarbonyl groups such as cycloalkoxycarbonyl and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methyloxalyl; thioalkyl groups; alkylthioalkyl groups such as methylthioalkyl and tert-butylthioalkyl; arylthioalkyl groups such as phenylthioalkyl and p-tolylthioalkyl; alkylsulfonyl groups; arylsulfonyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfonyl groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups, etc. Furthermore, when these substituents may further have more than one substituent, groups having more than one substituent selected from the above substituents as the further substituent (e.g., monoalkylamino, dialkylamino, arylamino, trifluoromethyl, etc.) are also included in the example of substituent T.

[0063] Unless otherwise specified in this specification, the bonding direction of the divalent groups is not limited. For example, in the compound represented by the formula "XYZ", when Y is -COO-, Y can be -CO-O- or -O-CO-. The above compound can be "X-CO-OZ" or "XO-CO-Z".

[0064] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, specifically, it is a value calculated using software package 1 described below from a database of values ​​based on Hammett substituent constants and known literature values. All pKa values ​​described in this specification are values ​​calculated using this software package.

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

[0066] Alternatively, pKa can also be obtained using molecular orbital calculations. As a specific example of this method, calculating H in aqueous solution based on thermodynamic cycles can be used. + The method of calculating H is based on the dissociation free energy. + Methods for calculating the dissociation free energy include, for example, DFT (density functional theory), and various other methods have been reported in the literature, and are not limited to this. Furthermore, there are various software programs available for performing 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 using Gaussian16 based on DFT (density functional theory) is adopted.

[0068] In this specification, pKa refers to "pKa in aqueous solution" as previously stated, but in cases where the pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be used.

[0069] In this specification, "solid component" refers to any component contained in a photosensitive or radiosensitive linear resin composition that forms a photosensitive or radiosensitive linear film, excluding solvents. Furthermore, any component contained in a photosensitive or radiosensitive linear resin composition that forms a photosensitive or radiosensitive linear film is considered a solid component, even if it is in liquid form.

[0070] <Pattern Formation Method>

[0071] The pattern forming method of the present invention includes:

[0072] (1) A step of forming a film using a photosensitive radioactive or radioactive linear resin composition, wherein the photosensitive radioactive or radioactive linear resin composition contains a resin (A) whose polarity is increased by the action of an acid, a photoacid generator, an acid diffusion control agent, and a solvent, and at least one of the photoacid generator and the acid diffusion control agent contains a sulfonium cation and an anion having an iodine atom.

[0073] (2) The process of exposing the above-mentioned film; and

[0074] (3) The process of developing the above-exposed film using an organic treatment solution containing butyl acetate and hydrocarbons with 9 or more but less than 12 carbon atoms.

[0075] The details of the mechanism by which the pattern forming method of the present invention exhibits excellent exposure latitude (EL) and LWR performance have not yet been clarified, but the inventors speculate as follows. However, the present invention is not limited to the mechanisms speculated below.

[0076] In pattern formation using an organic solvent-based developing process employing a resist composition containing a resin whose polarity increases through the action of acid (acid-degradable resin), the absorption rate of EUV light, etc., increases when iodine atoms are introduced into at least one of the photoacid generator and the acid diffusion control agent, thus mitigating the effects of shot noise. Therefore, theoretically, improved LWR performance can be expected. Furthermore, the increased molecular weight of at least one of the photoacid generator and the acid diffusion control agent through the introduction of iodine atoms can suppress excessive acid diffusion, also contributing to improved EL performance. However, the increased affinity of at least one of the photoacid generator and the acid diffusion control agent to the developer through the introduction of iodine atoms allows the developer to easily penetrate the resist film, resulting in decreased contrast and reduced swelling resistance of the resist film after development. Therefore, there are instances where a significant improvement in actual LWR and EL performance is not observed. It is believed that in this invention, the use of an organic treatment solution with low affinity for iodine atoms and containing butyl acetate and hydrocarbons with 9 to 12 carbon atoms as the developer can inhibit the penetration and swelling of the developer in the resist film, thereby improving the performance of LWR and EL.

[0077] The following is a detailed description of each of the above processes.

[0078] [Process (1)]

[0079] Step (1) is a step of forming a film using a photosensitive radioactive or radioactive linear resin composition, wherein the photosensitive radioactive or radioactive linear resin composition contains a resin (A) whose polarity is increased by the action of an acid, a photoacid generator, an acid diffusion control agent, and a solvent, and at least one of the photoacid generator and the acid diffusion control agent contains a sulfonium cation and an anion having an iodine atom.

[0080] The photosensitive or radiosensitive linear resin composition used in step (1) is typically a photoresist composition. For convenience, the photosensitive or radiosensitive linear resin composition used in step (1) is also referred to as a "photoresist composition". Furthermore, the film formed in step (1) using the photosensitive or radiosensitive linear resin composition is typically a photoresist film. For convenience, the film formed using the photosensitive or radiosensitive linear resin composition is also referred to as a "photoresist film".

[0081] Details regarding the photosensitive radioactive or radiosensitive linear resin composition used in step (1) will be described later.

[0082] Step (1) is preferably a step of forming a resist film on a substrate using a resist composition.

[0083] As a method for forming a resist film on a substrate using a resist composition, for example, a method of coating the resist composition onto the substrate can be described.

[0084] If necessary, the resist composition is preferably filtered with a filter before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.03 μm or less, even more preferably 0.01 μm or less, and particularly preferably 0.005 μm or less. The lower limit of the filter pore size is not particularly limited and can be 0.001 μm or more.

[0085] There are no particular limitations on the material of the filter. When it is a polymer, it is preferably made of: polyolefins such as polyethylene (PE) and polypropylene (PP) (including high-density and ultra-high molecular weight); polyamides such as nylon 6 and nylon 66; polyimide (PI); polyamide-imide; polyesters such as polyethylene terephthalate; polyethersulfone; cellulose; polytetrafluoroethylene (PTFE), perfluoroalkoxyalkanes, and other polyfluorocarbons; derivatives of the above polymers; etc. More preferably, it is made of at least one selected from the group consisting of polyolefins, polyamides, polyimides, polyamide-imides, polyesters, polysulfones, cellulose, polyfluorocarbons, and derivatives thereof.

[0086] In addition to resin, it can also be diatomaceous earth, glass, etc.

[0087] Furthermore, the filter used to filter the corrosion resist composition can be a single filter or two or more filters used in combination. When two or more filters are used, they can be the same filter or different filters.

[0088] The photoresist composition can be applied to a substrate (e.g., silicon, silicon coated with silicon dioxide, etc.) used for manufacturing integrated circuit elements by a suitable coating method such as a spin coater or a coater. Spin coating using a spin coater is preferred. The rotation speed when performing spin coating using a spin coater is preferably 1000 to 3000 rpm (rotations per minute).

[0089] After coating the resist composition, the substrate can be dried to form a resist film. Furthermore, various substrate films (inorganic films, organic films, anti-reflective films, etc.) can be formed under the resist film as needed.

[0090] As a drying method, for example, drying by heating can be cited. Heating can be carried out using devices found in at least one of ordinary exposure machines and developing machines, or using a hot plate or the like. The heating temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is not particularly limited, but is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0091] The thickness of the resist film is not particularly limited, but from the viewpoint of forming finer patterns with higher precision, it is preferably 10 to 120 nm. Specifically, when using EUV exposure, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. Furthermore, when using ArF immersion exposure, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0092] A topcoat composition can be used to form a topcoat on top of the resist film.

[0093] The topcoat composition is preferably not mixed with the resist film and can be further uniformly coated on the resist film. The topcoat is not particularly limited and can be formed by conventionally known methods, for example, the topcoat can be formed based on the description in paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543.

[0094] For example, it is preferable to form a top coating containing an alkaline compound, such as that described in Japanese Patent Application Publication No. 2013-61648, on the resist film. Specific examples of alkaline compounds that may be contained in the top coating include alkaline compounds that may be contained in the resist composition.

[0095] In addition, the top coating is preferably a compound containing at least one group or bond selected from the group consisting of ether, thioether, hydroxyl, thiol, carbonyl and ester bonds.

[0096] [Process (2)]

[0097] Step (2) is a process of exposing the film (resist film) formed in step (1).

[0098] As a method of exposure, one example is irradiating the formed resist film with photochemical rays or radiation through a prescribed mask.

[0099] 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 a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm can be used. 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.

[0100] Baking (heating) is preferably performed after exposure and before development. Baking promotes the reaction of the exposed part, resulting in better sensitivity and pattern shape.

[0101] The heating temperature for baking is not particularly limited, but is preferably 80-150°C, more preferably 80-140°C, and even more preferably 80-130°C.

[0102] There is no particular limitation on the heating time for baking, but it is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.

[0103] Heating can be carried out using devices found in at least one of ordinary exposure machines and developing machines, or by using a hot plate or the like.

[0104] This process is also known as post-exposure baking.

[0105] [Process (3)]

[0106] Step (3) is a process of developing the film that was exposed in step (2) using an organic treatment liquid containing butyl acetate and hydrocarbons with 9 or more but less than 12 carbon atoms.

[0107] The hydrocarbons containing 9 or more and 12 or less carbon atoms in the organic treatment liquid used in step (3) are preferably at least one selected from the group consisting of alkanes, alkenes, alkynes and cycloalkanes, more preferably alkanes, even more preferably at least one selected from the group consisting of nonane, decane, undecane and dodecane, particularly preferably at least one selected from the group consisting of undecane and dodecane, and most preferably undecane.

[0108] When structural isomers exist, such as undecane or dodecane, hydrocarbons with 9 or more but less than 12 carbon atoms may contain structural isomers.

[0109] The organic treatment liquid may contain only one type of hydrocarbon with 9 to 12 carbon atoms, or it may contain two or more types.

[0110] With the organic treatment liquid as 100% by mass, the content of hydrocarbons with 9 or more and 12 or less carbon atoms in the organic treatment liquid (when it contains multiple hydrocarbons with 9 or more and 12 or less carbon atoms, the total amount) is preferably 1% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 25% by mass or less.

[0111] The organic treatment solution contains butyl acetate (n-butyl acetate).

[0112] With the total organic treatment liquid as 100% by mass, the content of butyl acetate in the organic treatment liquid is preferably 65% ​​by mass or more and 99% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and even more preferably 75% by mass or more and 90% by mass or less.

[0113] The mass ratio of butyl acetate to hydrocarbons with 9 or more but less than 12 carbon atoms in the organic treatment liquid (butyl acetate content / hydrocarbon content with 9 or more but less than 12 carbon atoms) is preferably 60 / 40 to 95 / 5, more preferably 70 / 30 to 95 / 5, even more preferably 80 / 20 to 90 / 10, and particularly preferably 90 / 10.

[0114] The organic treatment liquid may contain other components besides butyl acetate and hydrocarbons with 9 to 12 carbon atoms. Examples of these other components include water, organic solvents other than butyl acetate and hydrocarbons with 9 to 12 carbon atoms, surfactants, antioxidants, and alkaline compounds. Taking the total organic treatment liquid as 100% by mass, the content of other components in the organic treatment liquid is preferably 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 1% by mass or less, further preferably 0% by mass or more and 0.5% by mass or less, and particularly preferably 0% by mass (i.e., no other components are contained).

[0115] The development method in process (3) is not particularly limited. For example, the following methods can be used: immersing the resist film in a tank filled with developer (the above-mentioned organic processing liquid) for a certain period of time (immersion method); using surface tension to cause the developer to accumulate on the surface of the resist film and remain still for a certain period of time to develop the resist film (puddle method); spraying the developer onto the surface of the resist film (spraying method); and continuously spraying the developer onto a substrate rotating at a certain speed while scanning the developer ejection nozzle at a certain speed (dynamic distribution method).

[0116] Alternatively, after the developing process, a process can be implemented where the developing process is stopped while the solvent is being replaced with another solvent.

[0117] The development time is not particularly limited as long as the resin in the part to be removed is fully dissolved. It is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds.

[0118] The temperature of the developer is not particularly limited, but is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0119] By performing process (3), a resist pattern (also simply referred to as "pattern") is formed.

[0120] After step (3), rinsing can be performed.

[0121] The above-mentioned organic treatment solutions can be used for rinsing, or rinsing solutions other than the above-mentioned organic treatment solutions can be used for rinsing.

[0122] There are no particular restrictions on the rinsing solution other than the aforementioned organic processing solution, as long as it is a solution that does not dissolve the pattern; a solution containing a common organic solvent can be used. Preferably, the rinsing solution other than the aforementioned organic processing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0123] There are no particular limitations on the rinsing method. For example, methods such as continuously spraying rinsing liquid onto a substrate rotating at a certain speed (spin coating method), immersing the substrate in a tank filled with rinsing liquid for a certain period of time (immersion method), and spraying rinsing liquid onto the surface of the substrate (spraying method) can be mentioned.

[0124] Furthermore, the pattern forming method of the present invention may include a heating step (Post Bake) after step (3). This step removes the developer and rinsing solution remaining between and inside the pattern. In addition, this step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after step (3) may be performed at, for example, 40 to 250°C (preferably 90 to 200°C) for, for example, 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0125] Alternatively, the formed pattern can be used as a mask to perform etching on the substrate. That is, the pattern formed in step (3) can be used as a mask to process the substrate (or the lower film and substrate) to form a pattern on the substrate.

[0126] The processing method of the substrate (or the lower film and the substrate) is not particularly limited, but preferably a method of forming a pattern on the substrate by dry etching the substrate (or the lower film and the substrate) using the pattern formed in step (3) as a mask. Dry etching is not particularly limited, but preferably oxygen plasma etching.

[0127] The organic processing liquid, resist composition, and other materials (e.g., solvents, rinsing liquids, antireflective film forming compositions, topcoat forming compositions, etc.) used in the pattern forming method of the present invention are preferably free of impurities such as metals. The impurity content contained in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, further preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. There is no particular limitation on the lower limit of the impurity content, which can be 0 ppt or more. Examples of metallic impurities include, for example, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0128] 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.

[0129] In addition, as a method to reduce impurities such as metals contained in various materials, for example, methods such as selecting raw materials with low metal content as raw materials for various materials, filtering the raw materials for various materials with filters, and using Teflon (registered trademark) to form a lining in the device to carry out distillation under conditions that suppress contamination as much as possible.

[0130] Besides filtration, impurities can also be removed using adsorption materials, or a combination of filtration and adsorption materials can be used. Known adsorption materials can be used, such as inorganic adsorption materials like silica gel and zeolite, and organic adsorption materials like activated carbon. To reduce impurities such as metals contained in these materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing apparatus. The content of metal components contained in the used cleaning solution is preferably 100 mass ppt or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less. There is no particular limitation on the lower limit, but 0 mass ppt or more is preferred.

[0131] In organic processing and rinsing solutions, conductive compounds may be added to prevent malfunctions in the solution piping and various components (filters, O-rings, and tubing, etc.) caused by electrostatic charging and subsequent electrostatic discharge. There are no particular limitations on the conductive compound; methanol is an example. The amount added is not particularly limited, but from the viewpoint of maintaining preferred developing or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. There is no particular limitation on the lower limit of the amount of conductive compound added, which can be 0.01% by mass or more.

[0132] 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 chemical fluid piping. Similarly, antistatic-treated polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can also be used for filters and O-rings.

[0133] [Photosensitive or radiosensitive linear resin composition]

[0134] The photosensitive radioactive or radiosensitive linear resin composition used in process (1) will be described.

[0135] The photosensitive or radiosensitive linear resin composition (resist composition) used in step (1) is the following photosensitive or radiosensitive linear resin composition, which contains a resin (A) whose polarity is increased by the action of acid, a photoacid generator, an acid diffusion control agent, and a solvent, wherein at least one of the photoacid generator and the acid diffusion control agent contains a sulfonium cation and an anion having an iodine atom.

[0136] The resist composition can be a positive resist composition or a negative resist composition, preferably a negative resist composition. Furthermore, the resist composition is preferably a resist composition for organic solvent development.

[0137] The resist composition can be a chemically amplified resist composition or a non-chemically amplified resist composition, preferably a chemically amplified resist composition.

[0138] [Resin (A)]

[0139] The resist composition contains a resin (A) whose polarity increases through the action of acid (also simply referred to as "resin (A)").

[0140] (Repeating unit with acid-decomposing groups)

[0141] The resin (A) is preferably a repeating unit containing acid-degradable groups.

[0142] Acid-decomposing groups are groups whose polarity increases through decomposition by the action of acids.

[0143] Acid-degradable groups are typically groups that decompose under the action of acids to produce polar groups. Preferably, the acid-degradable groups have a structure that protects the polar groups with groups (leaving groups) that detach under the action of acids. The resin (A) is preferably one whose polarity increases under the action of acids, and whose solubility relative to organic solvents decreases.

[0144] Examples of such polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tri(alkylcarbonyl)methylene groups, and tri(alkylsulfonyl)methylene groups, as well as acidic groups such as alcoholic hydroxyl groups.

[0145] 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.

[0146] As a group that is released by the action of an acid, examples include groups represented by formulas (Y1) to (Y4).

[0147] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0148] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0149] Equation (Y3): -C(R) 36 (R) 37 (OR) 38 )

[0150] Equation (Y4): -C(Rn)(H)(Ar)

[0151] 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), at least two of Rx1 to Rx3 are preferably methyl.

[0152] Rx1 to Rx3 are each preferably represented by a straight-chain or branched alkyl group, and Rx1 to Rx3 are more preferably represented by a straight-chain alkyl group.

[0153] Two of Rx1 to Rx3 can be bonded together to form a single ring or multiple rings.

[0154] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0155] As for the cycloalkyl groups Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl are preferred.

[0156] The aryl group of Rx1 to Rx3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene.

[0157] As for the alkenyl group of Rx1 to Rx3, vinyl is preferred.

[0158] The ring formed by the two bonds of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by the two bonds of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl or adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0159] In the cycloalkyl groups formed by the bonding of two bonds in Rx1 to Rx3, 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 vinylidene. In these cycloalkyl groups, one or more of the ethylides constituting the cycloalkane ring can be replaced by vinylides.

[0160] The group represented by formula (Y1) or formula (Y2) is preferably formed by Rx1 being methyl or ethyl and Rx2 being bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0161] In the case of a photosensitive or radiosensitive linear resin composition, such as an EUV exposure resist composition, the alkyl, cycloalkyl, alkenyl, aryl groups represented by Rx1 to Rx3, and the ring formed by the bonding of two of Rx1 to Rx3, preferably further have fluorine or iodine atoms as substituents.

[0162] In formula (Y3), R 36 ~R 38 Each can be used independently to represent a hydrogen atom or a monovalent organic group. R 37 With R 38 They can bond with each other to form rings. Examples of monovalent organic groups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R 36 Hydrogen atoms are also preferred.

[0163] Furthermore, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups may contain heteroatoms such as oxygen atoms and / or groups containing heteroatoms such as carbonyl groups. For example, in the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups, one or more methylene groups may be substituted with heteroatoms such as oxygen atoms and / or groups containing heteroatoms such as carbonyl groups.

[0164] R 38 It can bond with another substituent in the main chain of the repeating unit to form a ring. R 38 The group formed by bonding with another substituent in the main chain of the repeating unit is preferably an alkylene group such as methylene.

[0165] In the case of photosensitive or radiosensitive linear resin compositions, such as resist compositions for EUV exposure, R 36 ~R 38 The monovalent organic group and R represent 37 With R 38 The rings formed by mutual bonding are preferably further substituents of fluorine or iodine atoms.

[0166] As formula (Y3), it is preferably a group represented by the following formula (Y3-1).

[0167] [Chemical Formula 1]

[0168]

[0169] Here, L Y1 and L Y2 Each can independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof (e.g., a combination of alkyl and aryl groups).

[0170] M Y1 Indicates a single bond or a divalent linker.

[0171] Q Y1 This indicates that a group may contain a heteroatom alkyl group, a heteroatom cycloalkyl group, a heteroatom aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (e.g., a group composed of alkyl and cycloalkyl groups).

[0172] In alkyl and cycloalkyl groups, for example, a methylene group may be substituted by a heteroatom such as an oxygen atom, or a heteroatom-containing group such as a carbonyl group.

[0173] Preferably L Y1 and L Y2 One of them is a hydrogen atom, and the other is an alkyl, cycloalkyl, aryl, or alkylene group combined with an aryl group.

[0174] Q Y1 MY1 and L Y1 At least two of them can be bonded to form a ring (preferably a 5- or 6-membered ring).

[0175] From the perspective of pattern miniaturization, L Y2 Preferred alkyl or tertiary alkyl groups are secondary alkyl groups, more preferably tertiary alkyl groups. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl, while examples of tertiary alkyl groups include tertiary butyl and adamantyl. In these configurations, the glass transition temperature (Tg) and activation energy are increased, thus ensuring the strength of the film and suppressing fogging.

[0176] In equation (Y3-1), * represents the bonding position.

[0177] In formula (Y4), Ar represents an aromatic cycloalkane group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond to each other to form a non-aromatic ring. Ar is preferably an aryl group.

[0178] From the viewpoint of excellent acid decomposition properties of repeating units, when a non-aromatic ring is directly bonded to a polar group (or its residues) in the leaving group that protects the polar group, the cyclizing atom in the non-aromatic ring that is adjacent to the cyclizing atom directly bonded to the polar group (or its residues) is preferably not a halogen atom such as a fluorine atom as a substituent.

[0179] In addition, the groups that are removed by the action of acid can also be 2-cyclopentenyl with substituents (alkyl, etc.) such as 3-methyl-2-cyclopentenyl, and cyclohexyl with substituents (alkyl, etc.) such as 1,1,4,4-tetramethylcyclohexyl.

[0180] As a repeating unit having an acid-decomposable group, it is also preferred to be a repeating unit represented by formula (A).

[0181] [Chemical Formula 2]

[0182]

[0183] L1 represents a divalent linking group 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 leaving group that is removed by the action of an acid and may have a fluorine or iodine atom. At least one of L1, R1, and R2 has a fluorine or iodine atom.

[0184] Examples of divalent linking groups represented by L1, which may have fluorine or iodine atoms, include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups (e.g., alkylene, cycloalkylene, alkenyl, and arylene groups), and linking groups formed by connecting multiple of these. Among these, L1 is preferably -CO-, arylene, or -arylene-alkylene-with fluorine or iodine atoms, more preferably -CO- or -arylene-alkylene-with fluorine or iodine atoms.

[0185] As an arylene group, phenylene is preferred.

[0186] The alkylene group can be linear or branched. There is no particular limitation on the number of carbon atoms in the alkylene group, but it is preferably 1 to 10, more preferably 1 to 3.

[0187] There is no particular limitation on the total number of fluorine and iodine atoms contained in the alkylene group having fluorine or iodine atoms, but it is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0188] The alkyl group represented by R1 can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in the alkyl group, but it is preferably 1 to 10, and more preferably 1 to 3.

[0189] The total number of fluorine and iodine atoms contained in the alkyl group having fluorine or iodine atoms represented by R1 is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0190] Alkyl groups represented by R1 may contain heteroatoms other than halogen atoms such as oxygen atoms.

[0191] As a leaving group represented by R2, which may have fluorine or iodine atoms, examples can be given of leaving groups represented by the above formulas (Y1) to (Y4) that have fluorine or iodine atoms.

[0192] As a repeating unit having an acid-degradable group, it is also preferred to be a repeating unit represented by formula (AI).

[0193] [Chemical Formula 3]

[0194]

[0195] In formula (AI), Xa1 represents a hydrogen atom or an alkyl group that may have substituents. T represents a single bond or a divalent linking group. Rx1 to Rx3 independently represent alkyl (linear or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (linear or branched), or aryl (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl (linear or branched), at least two of Rx1 to Rx3 are preferably methyl.

[0196] Two of Rx1 to Rx3 can bond together to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0197] As an alkyl group represented by Xa1, which can have substituents, examples include methyl or alkyl groups represented by -CH2-R. 11 The group indicated by R. 11 This indicates a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. As a group composed of R... 11 The monovalent organic group represented can be, for example, an alkyl group with 5 or fewer carbon atoms that can be substituted by a halogen atom, an acyl group with 5 or fewer carbon atoms that can be substituted by a halogen atom, and an alkoxy group with 5 or fewer carbon atoms that can be substituted by a halogen atom, preferably an alkyl group with 3 or fewer carbon atoms, more preferably a methyl group. As Xa1, it is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0198] Examples of divalent linking groups for T include alkylene groups, aromatic cycloalkanes, -COO-Rt- groups, and -O-Rt- groups. In these formulas, Rt represents an alkylene group or a cycloalkylene group.

[0199] T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0200] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0201] 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.

[0202] The aryl group of Rx1 to Rx3 is preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene.

[0203] As for the alkenyl group of Rx1 to Rx3, vinyl is preferred.

[0204] The cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. Polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are also preferred. Among these, a monocyclic cycloalkyl group with 5 to 6 carbon atoms is preferred.

[0205] In the cycloalkyl groups formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a heteroatom-containing group such as a carbonyl group, or a vinylidene. Additionally, in these cycloalkyl groups, one or more of the ethylides constituting the cycloalkane ring may be replaced by vinylides.

[0206] The repeating unit represented by formula (AI) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0207] 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). The number of carbon atoms in the substituents is preferably 8 or less.

[0208] As the repeating unit represented by formula (AI), the acid-degradable (meth)acrylate tertiary alkyl ester repeating unit is preferred (Xa1 represents a hydrogen atom or methyl group, and T represents a single bond repeating unit).

[0209] Resin (A) may contain repeating units having acid-degradable groups containing unsaturated bonds, as repeating units having acid-degradable groups.

[0210] As a repeating unit having an acid-degrading group containing an unsaturated bond, the repeating unit represented by formula (B) is preferred.

[0211] [Chemical Formula 4]

[0212]

[0213] 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 linking group 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.

[0214] Two of Ry1 to Ry3 can bond together to form monocyclic or polycyclic rings (monocyclic or polycyclic cycloalkyl, cycloalkenyl, etc.).

[0215] As an alkyl group represented by Xb, which can have substituents, examples include methyl groups or -CH2-R groups. 11 The group indicated by R. 11The group represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, acyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, and alkoxy groups with 5 or fewer carbon atoms that can be substituted by a halogen atom. Preferably, it is an alkyl group with 3 or fewer carbon atoms, and more preferably, it is a methyl group. As Xb, it is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0216] 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 alkylene group, a cycloalkylene group, or an aromatic cyclic group, preferably an aromatic cyclic group.

[0217] The L group is preferably -Rt- group, -CO- group, -COO-Rt-CO- group, or -Rt-CO- group. Rt may have substituents such as halogen atoms, hydroxyl groups, and alkoxy groups.

[0218] The alkyl groups of Ry1 to Ry3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0219] As for the cycloalkyl groups of Ry1 to Ry3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl and adamantyl are preferred.

[0220] The aryl groups of Ry1 to Ry3 are preferably aryl groups with 6 to 10 carbon atoms, for example, phenyl, naphthyl and anthracene.

[0221] As for the alkenyl groups of Ry1 to Ry3, vinyl groups are preferred.

[0222] The acetylenic group is preferred as the alkynyl group of Ry1 to Ry3.

[0223] As the cycloalkenyl group of Ry1 to Ry3, it is preferably a structure containing a double bond in part of a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl.

[0224] The cycloalkyl group formed by the bonding of two of 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 with 5 to 6 carbon atoms.

[0225] In the cycloalkyl or cycloalkenyl groups formed by the bonding of two bonds in Ry1 to Ry3, for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a carbonyl group, a heteroatom-containing group such as a -SO2- group or a -SO3- group, a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl or cycloalkenyl groups, one or more of the ethylides constituting the cycloalkane or cycloalkene ring may be substituted with vinylides.

[0226] The repeating unit represented by formula (B) is preferably, for example, Ry1 is methyl, ethyl, vinyl, allyl, or aryl, and Ry2 and Ry3 are bonded to form the above-mentioned cycloalkyl or cycloalkenyl.

[0227] 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). The number of carbon atoms in the substituents is preferably 8 or less.

[0228] As the repeating unit represented by formula (B), the preferred repeating units are acid-degradable tertiary methacrylate repeating units (Xb represents a hydrogen atom or methyl group, and L represents a -CO- group repeating unit), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (Xb represents a hydrogen atom or methyl group, and L represents a phenyl repeating unit), and acid-degradable styrene carboxylic acid tertiary ester repeating units (Xb represents a hydrogen atom or methyl group, and L represents a -Rt-CO- group (Rt is an aromatic group) repeating units).

[0229] As a specific example of a repeating unit having an acid-degrading group containing an unsaturated bond, the repeating unit described in International Publication No. 2022 / 024928,

[0067] to

[0071] , can be cited, for example. The above description is incorporated herein by reference.

[0230] The following are specific examples of repeating units having acid-degrading groups, but are not limited thereto. Furthermore, repeating units having the acid-degrading groups described in the examples described later are also preferred.

[0231] [Chemical Formula 5]

[0232]

[0233] The content of repeating units having acid-degradable groups is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more, relative to all repeating units in resin (A). Furthermore, the content of repeating units having acid-degradable groups is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, relative to all repeating units in resin (A).

[0234] The resin (A) may contain one or more repeating units with acid-degradable groups. When the resin (A) contains two or more repeating units with acid-degradable groups, it is preferable that their total content is within the above-mentioned preferred content range.

[0235] (Repeating units with acid groups)

[0236] The resin (A) is preferably composed of repeating units having acid groups.

[0237] As an acid group, for example, 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 are preferred.

[0238] In the above-mentioned hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms can be replaced by groups other than fluorine atoms (such as alkoxycarbonyl groups). As an acid group, -C(CF3)(OH)-CF2- formed in this way is also preferred. In addition, one or more fluorine atoms can be replaced by groups other than fluorine atoms to form a ring containing -C(CF3)(OH)-CF2-.

[0239] The repeating unit having an acid group is preferably a repeating unit that is different from the repeating unit having an acid-decomposable group mentioned above.

[0240] Repeating units with acid groups can have fluorine or iodine atoms.

[0241] Specific examples of repeating units having acid groups include, for instance, the repeating units described in International Publication No. 2022 / 024928,

[0088] to

[0089] and

[0103] to

[0110] . The above description is incorporated herein by reference.

[0242] The repeating unit having an acid group is preferably a repeating unit having a phenolic hydroxyl group.

[0243] The repeating unit having phenolic hydroxyl groups is preferably a repeating unit that is different from the repeating unit having acid-degradable groups mentioned above.

[0244] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (Pa1). The resin (A) preferably contains repeating units represented by the following formula (Pa1).

[0245] [Chemical Formula 6]

[0246]

[0247] In formula (Pa1),

[0248] R a1 and R a2 Each can be used to represent a hydrogen atom or a substituent independently.

[0249] L a1 Indicates a single bond or a divalent linker.

[0250] Ar a1 It represents an aromatic ring group.

[0251] Ar a1 With R a2 or L a1 They can be bonded by single bonds or via linking groups.

[0252] R X This indicates a substituent other than a hydroxyl group.

[0253] n represents an integer greater than 1 and less than 9.

[0254] m represents an integer greater than 0 and less than 8.

[0255] R in formula (Pa1) a1 and R a2 Each can be used to represent a hydrogen atom or a substituent independently.

[0256] R a1 and R a2 The substituents indicated are not particularly limited, but are preferably alkyl, cycloalkyl, halogen atom, cyano or alkoxycarbonyl.

[0257] R a1 and R a2 The alkyl group can be either straight-chain or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. The alkyl group may have substituents.

[0258] R a1 and R a2 The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15. The cycloalkyl group can be a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, or adamantyl. The cycloalkyl group may have substituents.

[0259] As R a1 and R a2 The halogen atom represented can be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom or an iodine atom.

[0260] As R a1 and R a2The alkyl group represented by the alkoxycarbonyl group can be either straight-chain or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. The alkoxycarbonyl group may have substituents.

[0261] L in formula (Pa1) a1 Indicates a single bond or a divalent linker.

[0262] As L a1 The divalent linking group represented is not particularly limited; for example, -COO- and -CONR can be cited. a3 - alkylene groups, or groups consisting of two or more of these groups. R a3 It represents a hydrogen atom or an alkyl group.

[0263] The alkylene group is not particularly limited, but is preferably an alkylene group with 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene. The alkylene group may have substituents.

[0264] As R a3 When referring to an alkyl group, examples of alkyl groups with 20 or fewer carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, with alkyl groups having 8 or fewer carbon atoms being preferred.

[0265] Ar in formula (Pa1) a1 This indicates an aromatic cyclic group, specifically an aromatic cyclic group with a (m+n+1) valence.

[0266] Ar a1 The aromatic cyclic group represented can be an aromatic hydrocarbon group or an aromatic heterocyclic group.

[0267] As an aromatic hydrocarbon group, it is preferably a group containing aromatic hydrocarbons with 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, or condensed tetraphenylene.

[0268] The aromatic heterocyclic group preferably contains at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms as the cyclic atom. Preferably, the aromatic heterocyclic group comprises a group containing 4 to 20 aromatic heterocycles such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

[0269] Ar a1 With R a2 or L a1They can be bonded by single bonds or via linking groups. Examples of linking groups include -O-, -S-, -CO-, -CO2-, -SO-, -SO2-, alkylene groups (preferably with 1 to 5 carbon atoms), alkenyl groups (preferably with 2 to 5 carbon atoms), and groups formed by combining two or more of these. Alkylene and alkenyl groups may have substituents.

[0270] R in formula (Pa1) X This indicates a substituent other than a hydroxyl group.

[0271] As R X The substituents represented include, for example, carboxyl, sulfonyl, cyano, halogen atom, hydrocarbon, amino, nitro, and groups formed by combining two or more of these.

[0272] As R X The hydrocarbon group represented may include, for example, alkyl (preferably 1 to 10 carbon atoms), cycloalkyl (preferably 5 to 15 carbon atoms), and alkenyl (preferably 2 to 10 carbon atoms).

[0273] R X The represented hydrocarbon group can have substituents. Additionally, when R... X When the represented hydrocarbon group contains -CH2-, at least one of -CH2- can be substituted by at least one selected from the group consisting of -O-, -CO-, -S- and -SO2-.

[0274] R X The substituents indicated are preferably those having halogen atoms. The halogen atom is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom.

[0275] In formula (Pa1), n ​​represents an integer of 1 or more and 9 or less, preferably an integer of 1 or more and 5 or less, and more preferably an integer of 1 or more and 4 or less.

[0276] In formula (Pa1), m represents an integer greater than or equal to 0 and less than or equal to 8, preferably an integer greater than or equal to 0 and less than or equal to 4, and more preferably an integer greater than or equal to 0 and less than or equal to 3.

[0277] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (Pa2). The resin (A) preferably contains repeating units represented by the following formula (Pa2).

[0278] [Chemical Formula 7]

[0279]

[0280] In formula (Pa2),

[0281] R a4 It represents a hydrogen atom or an alkyl group.

[0282] L a2 This indicates a single bond or -COO-.

[0283] R X1 It represents a halogen atom, a haloalkyl group, or a hydrocarbon group.

[0284] n1 represents an integer greater than or equal to 1 and less than or equal to 5.

[0285] m1 represents an integer greater than 0 and less than 4.

[0286] r represents an integer greater than 0 and less than 3.

[0287] R in formula (Pa2) a4 It represents a hydrogen atom or an alkyl group.

[0288] R a4 The alkyl group can be either straight-chain or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. The alkyl group may have substituents.

[0289] L in formula (Pa2) a2 It represents a single bond or -COO-, preferably a single bond.

[0290] In formula (Pa2), r represents an integer greater than or equal to 0 and less than or equal to 3, preferably an integer greater than or equal to 0 and less than or equal to 2, more preferably 0 or 1, and even more preferably 0. As an aromatic ring in formula (Pa2), when r represents 0, it is benzene; when r represents 1, it is naphthalene; when r represents 2, it is anthracene; and when r represents 3, it is condensed tetraphenylene.

[0291] R in formula (Pa2) X1 It represents a halogen atom, a haloalkyl group, or a hydrocarbon group.

[0292] As R X1 The halogen atom represented is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0293] As R X1 The alkyl halogroup referred to is preferably a alkyl halogroup having 1 to 10 carbon atoms, and more preferably a alkyl halogroup having 1 to 5 carbon atoms. The alkyl halogroup can be a alkyl halogroup in which some hydrogen atoms of the alkyl group are replaced by halogen atoms, or a fully alkyl halogroup in which all hydrogen atoms of the alkyl group are replaced by halogen atoms. The alkyl halogroup is preferably a fluoroalkyl group.

[0294] As R X1The hydrocarbon group represented may include, for example, alkyl (preferably 1 to 10 carbon atoms), cycloalkyl (preferably 5 to 15 carbon atoms), and alkenyl (preferably 2 to 10 carbon atoms).

[0295] R X1 The represented hydrocarbon group and haloalkyl group can have substituents. Additionally, when R... X1 When the represented hydrocarbon group and haloalkyl group contain -CH2-, at least one of -CH2- can be replaced by at least one selected from the group consisting of -O-, -CO-, -S- and -SO2-.

[0296] In formula (Pa2), n1 represents an integer greater than or equal to 1 and less than or equal to 5, and preferably represents an integer greater than or equal to 1 and less than or equal to 4.

[0297] In formula (Pa2), m1 represents an integer greater than or equal to 0 and less than or equal to 4, and preferably represents an integer greater than or equal to 0 and less than or equal to 3.

[0298] The following are specific examples of repeating units having acid groups, but are not limited to these. In the following structural formula, G 1 and G 2 Each of the following can be independently represented: hydrogen atom, methyl group, fluorine atom, chlorine atom, trifluoromethyl group, cyano group, hydroxyl group, or hydroxymethyl group. f1 represents an integer from 1 to 3. Alternatively, repeating units having acid groups, as described in the examples below, are also preferred.

[0299] [Chemical Formula 8]

[0300]

[0301] When resin (A) contains repeating units having acid groups, the content of repeating units having acid groups is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in resin (A). Furthermore, the content of repeating units having acid groups is preferably 90 mol% or less, more preferably 80 mol% or less, relative to all repeating units in resin (A).

[0302] (A repeating unit that has a fluorine, bromine, or iodine atom but does not have an acid-decomposing group or any of the acid groups)

[0303] In addition to the aforementioned <repeating units with acid-decomposable groups> and <repeating units with acid groups>, resin (A) may also contain repeating units (hereinafter also referred to as unit X) that do not have either acid-decomposable groups or acid groups but have fluorine, bromine, or iodine atoms. The <repeating units with fluorine, bromine, or iodine atoms that do not have either acid-decomposable groups or acid groups> are preferably different from other types of repeating units belonging to group A, such as <repeating units with lactone, sulopentalide, or carbonate groups> and <repeating units with photoacid-generating groups>, which are described later.

[0304] As unit X, it is preferably a repeating unit represented by formula (C).

[0305] [Chemical Formula 9]

[0306]

[0307] L5 represents a single bond or an ester group. R9 represents a hydrogen atom, or an alkyl group that may have fluorine or iodine atoms. 10 It represents a hydrogen atom, an alkyl group that may have a fluorine atom or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, or a group composed of these.

[0308] Specific examples of repeating units having fluorine or iodine atoms include, for example, the repeating units described in International Publication No. 2022 / 024928,

[0116] to

[0117] . The above description is incorporated herein by reference.

[0309] The content of unit X relative to all repeating units in resin (A) is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. Furthermore, as an upper limit, it is preferably 80 mol% or less relative to all repeating units in resin (A), more preferably 70 mol% or less.

[0310] In the repeating units of resin (A), the total content of repeating units having 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 particularly 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).

[0311] Furthermore, as a repeating unit having at least one of fluorine, bromine, and iodine atoms, examples include repeating units having fluorine, bromine, or iodine atoms and having acid-decomposing groups; repeating units having fluorine, bromine, or iodine atoms and having acid groups; and repeating units having fluorine, bromine, or iodine atoms.

[0312] (Repeating units with lactone, sulcinolone, or carbonate groups)

[0313] Resin (A) may have repeating units (hereinafter also referred to as "unit Y") containing at least one selected from the group consisting of lactone groups, sulcinolone groups and carbonate groups.

[0314] Unit Y is preferably free of acid groups such as hydroxyl and hexafluoropropanol groups.

[0315] The lactone group or sulfonolactone group can be used as long as it has a lactone structure or a sulfonolactone structure. The lactone structure or sulfonolactone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sulfonolactone structure. More preferably, the 5- to 7-membered ring lactone structure has other ring structures formed by ring condensation on the ring in the form of a bicyclic structure or a spirocyclic structure, or the 5- to 7-membered ring sulfonolactone structure has other ring structures formed by ring condensation on the ring in the form of a bicyclic structure or a spirocyclic structure.

[0316] Resin (A) preferably contains repeating units having a lactone group, a sulopentalide group, or a carbonate group, wherein the lactone group, sulopentalide group, or carbonate group is formed by removing one or more hydrogen atoms from the cyclizing atoms of a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-22), a sulopentalide structure represented by any one of the following formulas (SL1-1) to (SL1-3), or a cyclic carbonate structure represented by any one of the following formulas (CC1-1) to (CC1-2). The lactone group, sulopentalide group, or carbonate group can be directly bonded to the main chain. For example, the cyclizing atoms of the lactone group, sulopentalide group, or carbonate group can constitute the main chain of resin (A). The lactone group, sulopentalide group, and carbonate group may have substituents.

[0317] R in the following structural formula L Indicates a substituent. When R L When multiple R exist, multiple R L They can be the same or different. As R... L Examples include alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 4 to 10 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 2 to 8 carbon atoms, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. e1 represents an integer from 0 to 4. When multiple e1s exist, they can be the same or different. When e1 is 2 or more, multiple Rs exist. LR can be the same or different; there can be multiple R. L They can also bond together to form a ring.

[0318] [Chemical Formula 10]

[0319]

[0320] As a repeating unit having a lactone group, a sulcinolone group or a carbonate group, for example, a repeating unit represented by the following formula (AI-2) can be cited.

[0321] [Chemical Formula 11]

[0322]

[0323] In formula (AI-2), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. The alkyl group of Rb0 may have substituents. Preferred substituents that the alkyl group of Rb0 may have include hydroxyl groups and halogen atoms.

[0324] Examples of halogen atoms that can be represented by Rb0 include fluorine, chlorine, bromine, and iodine. Rb0 is preferably represented by hydrogen or methyl atoms.

[0325] Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group composed of these. Preferably, Ab is a single bond or a linking group represented by -Ab1-CO2-. Ab1 is a straight-chain or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably methylene, ethylene, cyclohexylene, adamantylene, or norbornylene.

[0326] V represents a group formed by removing a hydrogen atom from the cyclic atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-22), a group formed by removing a hydrogen atom from the cyclic atom of a sulfonolactone structure represented by any one of formulas (SL1-1) to (SL1-3), or a group formed by removing a hydrogen atom from the cyclic atom of a cyclic carbonate structure represented by any one of formulas (CC1-1) to (CC1-2).

[0327] When an optical isomer is present in a repeating unit having a lactone group or a sulcinolone group, any one of the optical isomers can be used. Alternatively, a single optical isomer can be used alone, or multiple optical isomers can be used in combination. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, more preferably 95 or higher.

[0328] As a carbonate group, a cyclic carbonate group is preferred.

[0329] Regarding repeating units having cyclic carbonate groups, for example, refer to the descriptions in International Publication No. 2022 / 024928,

[0127] to

[0133] . The above descriptions are incorporated herein by reference.

[0330] When resin (A) contains unit Y, 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 80 mol% or less, more preferably 70 mol% or less, relative to all repeating units in resin (A).

[0331] (Repeating unit with photoacid-generating group)

[0332] Resin (A) may contain repeating units with groups that produce acid upon exposure to photochemical rays or radiation (also known as "photoacid-producing groups").

[0333] As a repeating unit with a photoacid-generating group, the repeating unit represented by equation (4) can be cited.

[0334] [Chemical Formula 12]

[0335]

[0336] R 41 This indicates a hydrogen atom or a methyl group. L 41 Indicates a single bond or a divalent linker. L 42 Represents a divalent linker group. R 40 This indicates the structural sites that decompose upon exposure to photochemical rays or radiation, resulting in the formation of acids in the side chains.

[0337] L 41 The linking group represents a single bond or a divalent bond, preferably a single bond or an ester bond (-COO-).

[0338] L 42 Preferably, it is a linking group consisting of at least one selected from the group consisting of alkylene, cycloalkylene, arylene, -O-, -CO-, -S-, -SO-, -SO2-, and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as alkyl, cycloalkyl, aryl, etc.).

[0339] The alkylene group can be either straight-chain or branched. There is no particular limitation on the number of carbon atoms in the alkylene group, but it is preferably 1 to 10.

[0340] The cycloalkylene group can be a monocyclic or polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15.

[0341] There is no particular limitation on the number of carbon atoms in the arylene group, but it is preferably 6 to 20, and more preferably 6 to 10.

[0342] Alkylene, cycloalkylene, and arylene can have substituents, and the above-mentioned substituent T can be cited as an example of a substituent.

[0343] R 40 Preferably, it is a group represented by the following formula (S4-1).

[0344] [Chemical Formula 13]

[0345]

[0346] In formula (S4-1), Q - M represents an acid residue. + * indicates a cation. * indicates a reaction with L 41 The bonding positions.

[0347] The so-called acid residues refer to the groups formed by the dissociation of a proton from an acid.

[0348] Q - Preferably, it is a carboxylate anion group (COO) - ), sulfonate anion group (SO3) - ), or sulfonamide group (from N - -SO2R N1 Indicates. R N1 The organic group can be exemplified by organic groups having 1 to 10 carbon atoms, preferably alkyl, fluoroalkyl, or aryl groups. More preferably, it is a sulfonate anion group.

[0349] Regarding M + The description, specific examples, and preferred range of M are consistent with the description of photoacid generators. + same.

[0350] Specific examples of repeating units having photoacid-generating groups include, for instance, the repeating units described in

[0094] to

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

[0094] of International Publication No. 2018 / 193954, and the repeating units described in

[0138] of International Publication No. 2022 / 024928. The above descriptions are incorporated herein by reference.

[0351] As a repeating unit represented by equation (4), examples include the repeating unit described in paragraphs

[0094] to

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

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

[0352] When resin (A) contains repeating units having photoacid-generating groups, the content of repeating units having photoacid-generating groups relative to all repeating units in resin (A) is preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more. Furthermore, the content of repeating units having photoacid-generating groups relative to all repeating units in resin (A) is preferably 50 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less.

[0353] Resin (A) is also preferably free of repeating units having photoacid generating groups.

[0354] (Repeating units represented by equation (V-1) or equation (V-2))

[0355] Resin (A) may have repeating units represented by the following formula (V-1) or the following formula (V-2).

[0356] The repeating unit represented by the following formula (V-1) and the following formula (V-2) is preferably a repeating unit that is different from the repeating unit described above.

[0357] [Chemical Formula 14]

[0358]

[0359] In the formula,

[0360] R6 and R7 independently represent a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR or -COOR: R is an alkyl group or fluorinated alkyl group with 1 to 6 carbon atoms), or carboxyl group. As an alkyl group, it is preferably a straight-chain, branched, or cyclic alkyl group with 1 to 10 carbon atoms.

[0361] n3 represents an integer from 0 to 6.

[0362] n4 represents an integer from 0 to 4.

[0363] X4 represents a methylene group, an oxygen atom, or a sulfur atom.

[0364] The following examples illustrate repeating units represented by equations (V-1) or (V-2).

[0365] 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.

[0366] (Repetitive units used to reduce the mobility of the main chain)

[0367] From the viewpoint of suppressing excessive diffusion of acid or pattern collapse during development, resin (A) preferably has a high glass transition temperature (Tg). Tg is preferably above 90°C, more preferably above 100°C, even more preferably above 110°C, and particularly preferably above 125°C. Furthermore, from the viewpoint of excellent dissolution rate in the developer, Tg is preferably below 400°C, more preferably below 350°C.

[0368] Furthermore, in this specification, the glass transition temperature (Tg) of polymers such as resin (A) (hereinafter referred to as "Tg of repeating units") 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 these values ​​are summed to obtain the Tg (°C) of the polymer.

[0369] The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). The Tg obtained by the Bicerano method can be calculated using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0370] Regarding the repeating units used to reduce the mobility of the main chain, refer to the contents of International Publication No. 2022 / 024928,

[0144] to

[0160] .

[0371] (A repeating unit having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano and base-soluble groups)

[0372] Resin (A) may contain repeating units having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano and base-soluble groups.

[0373] Examples of repeating units containing lactone, sulfonyl, or carbonate groups in resin (A) include those described in the section on "Repeating Units Containing Lactone, Sulfolactone, or Carbonate Groups" above. The preferred content is also as described in the section on "Repeating Units Containing Lactone, Sulfolactone, or Carbonate Groups" above.

[0374] Resin (A) may contain repeating units with hydroxyl or cyano groups. This improves the substrate adhesion.

[0375] The repeating unit having a hydroxyl or cyano group is preferably a repeating unit containing a saturated hydrocarbon group having a hydroxyl or cyano group (substituted by a hydroxyl or cyano group). Alternatively, it may be a repeating unit having an alicyclic hydrocarbon structure substituted by a hydroxyl or cyano group.

[0376] 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.

[0377] Resin (A) may contain repeating units with alkali-soluble groups.

[0378] Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide 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 having alkali-soluble groups in the resin (A), the resolution in contact hole applications is improved. Examples of repeating units having alkali-soluble groups include the repeating units described in paragraphs

[0085] and

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

[0379] (A repeating unit with an alicyclic hydrocarbon structure that does not exhibit acid decomposition properties)

[0380] Resin (A) may contain repeating units with an alicyclic hydrocarbon structure that do not exhibit acid-degrading properties. This reduces the leaching of low-molecular-weight components from the resist film into the immersion solution during immersion exposure. Examples of repeating units with an alicyclic hydrocarbon structure that do not exhibit acid-degrading properties include, for example, repeating units derived from 1-adamantane (meth)acrylate, diadamantane (meth)acrylate, tricyclodecyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0381] (A repeating unit represented by formula (III) that does not have either a hydroxyl or a cyano group)

[0382] Resin (A) may contain repeating units represented by formula (III) that do not have either hydroxyl or cyano groups.

[0383] [Chemical Formula 15]

[0384]

[0385] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and not having either a hydroxyl or a cyano group.

[0386] Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.

[0387] 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.

[0388] (Other repeating units)

[0389] In addition, resin (A) may have other repeating units besides the repeating units described above.

[0390] For example, resin (A) may have repeating units selected from the group consisting of repeating units having an oxathiane ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group.

[0391] In addition to the repeating structural units mentioned above, resin (A) may also have various repeating structural units for purposes such as adjusting dry etching resistance, standard developer compatibility, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0392] As resin (A), particularly when the resist composition is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, it is preferable that all repeating units are composed of repeating units derived from compounds having ethylene unsaturated bonds. In particular, it is also preferable that all repeating units are composed of (meth)acrylate repeating units. When all repeating units are composed of (meth)acrylate repeating units, repeating units in which all repeating units are methacrylate repeating units, repeating units in which all repeating units are acrylate repeating units, or repeating units in which all repeating units are composed of methacrylate repeating units and acrylate repeating units can be used, preferably with acrylate repeating units accounting for 50 mol% or less of all repeating units.

[0393] A preferred embodiment of the present invention is that the resin (A) comprises repeating units having iodine atoms. By including repeating units having iodine atoms in the resin (A), the absorption rate of EUV light, etc., is increased, the influence of shot noise can be reduced, and the LWR performance is further improved.

[0394] Resin (A) can be synthesized using conventional methods (such as free radical polymerization).

[0395] The weight-average molecular weight (Mw) of resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000, calculated by GPC method using polystyrene equivalents.

[0396] The dispersion (molecular weight distribution, Mw / Mn) of resin (A) is preferably 1.0 to 5, more preferably 1.0 to 3, even more preferably 1.1 to 2.0, and particularly preferably 1.1 to 1.5. The smaller the dispersion, the better the resolution and resist shape, and the smoother the sidewalls of the resist pattern, and the better the roughness.

[0397] The content of resin (A) in the resist composition is preferably 30.0 to 99.9% by mass, more preferably 40.0 to 99.9% by mass, and even more preferably 60.0 to 90.0% by mass, relative to the total solid content of the resist composition.

[0398] Resin (A) can be used alone or in combination with two or more resins. When two or more resins are used, it is preferable that their total content is within the range of the preferred content described above.

[0399] [Photoacid Generator]

[0400] The resist composition contains a photoacid generator.

[0401] Photoacid generators are compounds that produce acids through exposure to photochemical rays or radiation.

[0402] The photoacid generator can be a compound that is different from or the same as the resin (A).

[0403] The photoacid generator can be a different compound from the acid diffusion control agent, or it can be the same compound, but preferably a different compound.

[0404] The photoacid generator is preferably at least one selected from the group consisting of -O-CO-, -O-CO-O- and -O-.

[0405] The preferred photoacid generator is a compound that produces an acid with a pKa less than 0 by irradiation with photochemical rays or radiation.

[0406] The pKa of acids generated from photoacid generators by irradiation with photochemical rays or radiation is preferably -0.1 or less, more preferably -0.2 or less. Furthermore, the pKa of acids generated from photoacid generators by irradiation with photochemical rays or radiation is preferably -1.5 or more, more preferably -1.0 or more.

[0407] The photoacid generator can be in the form of a low-molecular-weight compound or in a form incorporated into the polymer. Alternatively, it can be in both the low-molecular-weight compound form and the form incorporated into the polymer.

[0408] When the photoacid generator is in the form of a low molecular weight compound, there is no particular limitation on the molecular weight of the photoacid generator. It is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000.

[0409] When the photoacid generating agent is incorporated into a portion of the polymer, it can be incorporated into a portion of resin (A) or into a resin different from resin (A). When resin (A) does not contain the aforementioned repeating unit having a photoacid generating group, the resist composition preferably contains a photoacid generating agent as a compound different from resin (A). When resin (A) contains repeating units having a photoacid generating group, the resist composition may additionally contain a photoacid generating agent, but preferably does not contain a photoacid generating agent.

[0410] The photoacid generator is preferably in the form of a low molecular weight compound.

[0411] The photoacid generator is preferably a compound represented by the following formula (T-1).

[0412] [Chemical Formula 16]

[0413]

[0414] In equation (T-1),

[0415] R T1 It represents a hydrogen atom or a substituent.

[0416] L T1 Indicates a single bond or a linking group.

[0417] X T1 It indicates alkylene, cycloalkylene, arylene, or heteroarylene.

[0418] M1 + It represents a sulfonium cation.

[0419] Among them, R T1 L T1 and X T1 At least one of them contains an iodine atom.

[0420] L in equation (T-1) T1 Indicates a single bond or a linking group.

[0421] L T1The linking group is not particularly limited, and examples include -O-, -S-, -CO-, -O-CO-, -O-CO-O-, -SO-, -SO2-, -SO-, -NR-, -NR-CO-, -CO-NR-CO-, -NR-SO2-, alkylene, cycloalkylene, arylene, heteroarylene, and groups formed by combining two or more of these. R represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group (preferably with 1 to 10 carbon atoms), a cycloalkyl group (preferably with 3 to 15 carbon atoms), or an aryl group (preferably with 6 to 15 carbon atoms). R can be combined with R... T1 or X T1 They bond together to form a ring.

[0422] As L T1 The alkylene group represented is not particularly limited, but is preferably an alkylene group with 1 to 10 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene, and more preferably an alkylene group with 1 to 6 carbon atoms. T1 The alkylene group represented may have substituents.

[0423] L T1 The number of carbon atoms in the represented cycloalkyl group is not particularly limited; for example, it is preferably 3 to 20, more preferably 4 to 15. The cycloalkyl group can be a monocyclic cycloalkyl group such as cyclopentylene or cyclohexylene, or a polycyclic cycloalkyl group such as norbornylene, tetracyclodecylene, tetracyclododecylene, or adamantylene. One or more methylene groups in the cycloalkane ring constituting the cycloalkyl group can be substituted with heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, or ester bonds, or with vinylene groups. Furthermore, one or more ethylene groups in the cycloalkane ring constituting the cycloalkyl group can be substituted with vinylene groups. T1 The cycloalkylene groups represented may have substituents.

[0424] As L T1 The arylene group represented is not particularly limited; for example, arylene groups with 6 to 20 carbon atoms can be cited, with arylene groups with 6 to 15 carbon atoms being preferred. As an arylene group, phenylene or naphthylene is preferred, with phenylene being particularly preferred. T1 The arylene group represented may have substituents.

[0425] As L T1 The heteroaryl group represented is not particularly limited; for example, it is preferably a heteroaryl group with 3 to 19 carbon atoms, and more preferably a heteroaryl group with 4 to 14 carbon atoms. The heteroaryl group preferably includes at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as the cyclic atom. T1 The number of cyclic atoms in the represented heteroaryl group is preferably 4 to 20, more preferably 5 to 15. T1The heteroaryl group represented may have substituents.

[0426] L T1 Preferably, it includes at least one selected from the group consisting of -O-CO-, -O-CO-O- and -O-.

[0427] X in equation (T-1) T1 It indicates alkylene, cycloalkylene, arylene, or heteroarylene.

[0428] As X T1 The alkylene group represented is not particularly limited, but is preferably an alkylene group with 1 to 10 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene, and more preferably an alkylene group with 1 to 6 carbon atoms.

[0429] X T1 The alkylene group may have substituents. Substituents are not particularly limited, for example, the substituent T mentioned above, preferably a halogen atom, cycloalkyl, aryl, etc., more preferably a fluorine atom or an iodine atom, and even more preferably a fluorine atom.

[0430] X T1 The number of carbon atoms in the represented cycloalkyl group is not particularly limited; for example, it is preferably 3 to 20, more preferably 4 to 15. The cycloalkyl group can be a monocyclic cycloalkyl group such as cyclopentylene or cyclohexylene, or a polycyclic cycloalkyl group such as norbornylene, tetracyclodecylene, tetracyclododecylene, or adamantylene. One or more methylene groups in the cycloalkane ring constituting the cycloalkyl group can be substituted with heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, or ester bonds, or with vinylene groups. Furthermore, one or more ethylene groups in the cycloalkane ring constituting the cycloalkyl group can be substituted with vinylene groups.

[0431] X T1 The cycloalkylene group represented may have substituents. Substituents are not particularly limited; for example, the substituent T mentioned above is preferred, preferably a halogen atom, alkyl group, aryl group, etc., more preferably a fluorine atom or iodine atom, and even more preferably a fluorine atom.

[0432] As X T1 The arylene group represented is not particularly limited; for example, arylene groups with 6 to 20 carbon atoms can be cited, and arylene groups with 6 to 15 carbon atoms are preferred. As an arylene group, phenylene or naphthylene is preferred, and phenylene is particularly preferred.

[0433] X T1 The arylene group may have substituents. Substituents are not particularly limited; for example, the substituent T mentioned above is preferred, preferably a halogen atom, alkyl group, cycloalkyl group, etc., more preferably a fluorine atom or iodine atom, and even more preferably a fluorine atom.

[0434] As X T1 The heteroaryl group represented is not particularly limited; for example, it is preferably a heteroaryl group with 3 to 19 carbon atoms, and more preferably a heteroaryl group with 4 to 14 carbon atoms. The heteroaryl group preferably includes at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a cyclic atom. T1 The number of cyclic atoms of the heteroaryl group represented is preferably 4 to 20, more preferably 5 to 15.

[0435] X T1 The heteroaryl group represented may have substituents. Substituents are not particularly limited; for example, the substituent T mentioned above is preferred, preferably a halogen atom, alkyl group, cycloalkyl group, etc., more preferably a fluorine atom or iodine atom, and even more preferably a fluorine atom.

[0436] X T1 Preferably, it represents an alkylene or arylene, more preferably an alkylene having a fluorine atom or an arylene having a fluorine atom.

[0437] R in equation (T-1) T1 It represents a hydrogen atom or a substituent.

[0438] R T1 The substituents represented are not particularly limited. For example, the above-mentioned substituent T can be cited, preferably halogen atoms, alkyl, alkoxy, alkylthio, cycloalkyl, cycloalkoxy, cycloalkylthio, aryl, heteroaryl, aryloxy, arylthio, etc.

[0439] R T1 The halogen atom represented is preferably a fluorine atom, chlorine atom, bromine atom, or iodine atom, more preferably a fluorine atom or iodine atom, and even more preferably an iodine atom.

[0440] R T1 The alkyl group can be either straight-chain or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have substituents. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and trifluoromethyl.

[0441] Regarding R T1 The description, specific examples, and preferred range of the alkyl groups included in the alkoxy and alkathioyl groups represented are consistent with those of the above-mentioned R. T1 The alkyl groups represented are the same.

[0442] R T1The cycloalkyl group can be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, more preferably 4 to 15. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. The cycloalkyl group may have substituents. One or more methylene groups in the cycloalkane ring constituting the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, ester bonds, or vinylidenes. Furthermore, one or more ethylides constituting the cycloalkane ring in the cycloalkyl group may be substituted with vinylides.

[0443] Regarding R T1 The description, specific examples, and preferred range of the cycloalkyl groups contained in the cycloalkoxy and cycloalkylthio groups represented are consistent with those of the above-mentioned R. T1 The cycloalkyl groups represented are the same.

[0444] R T1 The aryl group represented is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, further preferably phenyl or naphthyl, and particularly preferably phenyl. The aryl group may have substituents.

[0445] Regarding R T1 The description, specific examples, and preferred range of the aryl groups contained in the aryloxy and arylthyl groups represented are consistent with those of the above-mentioned R. T1 The aryl groups represented are the same.

[0446] R T1 The heteroaryl group represented is preferably a heteroaryl group with 3 to 19 carbon atoms, more preferably a heteroaryl group with 4 to 14 carbon atoms. The heteroaryl group preferably includes at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a cyclic atom. T1 The heteroaryl group represented preferably has 4 to 20 cyclic atoms, more preferably 5 to 15. Examples of heteroaryl groups include pyrrole, furanyl, thiophene, indolyl, benzofuranyl, and benzothiophene. The heteroaryl group may have substituents.

[0447] Wherein, R in equation (T-1) T1 L T1 and X T1 At least one of them contains an iodine atom. R T1 L T1 and X T1 The total number of iodine atoms contained is one or more, preferably two or more.

[0448] R T1 and X T1 At least one of them preferably contains an iodine atom, more preferably R T1 Contains iodine atoms. As R T1 Examples of ways that include iodine atoms include R.T1 The way iodine atoms are represented, R T1 The substituents represented (e.g., alkyl, alkoxy, alkylthio, cycloalkyl, cycloalkoxy, cycloalkylthio, aryl, heteroaryl, aryloxy, arylthio, etc.) have iodine atoms in a manner that...

[0449] M1 in equation (T-1) + It represents a sulfonium cation.

[0450] M1 + The sulfonium cation represented is preferably one having a halogen atom, and more preferably one having a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0451] As M1 + The sulfonium cation represented is preferably a cation represented by the formula (ZaI) (hereinafter also referred to as "cation (ZaI)").

[0452] [Chemical Formula 17]

[0453]

[0454] In the above formula (ZaI), R 201 R 202 and R 203 Each organic group can be represented independently.

[0455] As R 201 R 202 and R 203 The organic group preferably has 1 to 30 carbon atoms, more preferably 1 to 20. 201 ~R 203 The two atoms in R can bond together to form a ring structure, or the ring can contain oxygen atoms, sulfur atoms, ester groups, amide groups, or carbonyl groups. 201 ~R 203 Two groups formed by bonding in the middle, for example, alkylene (e.g., butylene and pentyleene) and -CH2-CH2-O-CH2-CH2-.

[0456] Preferred cations represented by the formula (ZaI) include cations (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.

[0457] First, the cation (ZaI-1) will be explained.

[0458] The cation (ZaI-1) is an arylsulfonium cation, wherein R in the above formula (ZaI) 201 ~R 203 At least one of them is an aryl group.

[0459] The arylsulfonium cation can be R 201 ~R 203 All of them are aryl, or they can be R. 201 ~R 203 A portion of it is aryl, and the remainder is alkyl or cycloalkyl.

[0460] It can be R 201 ~R 203 One of them is aryl, R 201 ~R 203 The remaining two bonds in the ring form a ring structure, or the ring may contain oxygen atoms, sulfur atoms, ester groups, amide groups, or carbonyl groups. As R 201 ~R 203 Two groups formed by bonding in the alkyl group, for example, alkylene groups (e.g., butylene, pentylene, and -CH2-CH2-O-CH2-CH2-), wherein one or more methylene groups may be substituted by an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group.

[0461] Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and arylbicycloalkylsulfonium cations.

[0462] The aryl group contained in the arylsulfonium cation is preferably phenyl or naphthyl, more preferably phenyl. The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups can be the same or different.

[0463] The alkyl or cycloalkyl group of the arylsulfonium cation is preferably a straight-chain alkyl group with 1 to 15 carbon atoms, a branched alkyl group with 3 to 15 carbon atoms, or a cycloalkyl group with 3 to 15 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, or cyclohexyl.

[0464] As R 201 ~R 203 The aryl, alkyl, and cycloalkyl groups may have substituents, 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 atom (e.g., fluorine and iodine), hydroxyl, carboxyl, ester, sulfinyl, sulfonyl, alkylthio, or phenylthio.

[0465] If possible, the above-mentioned substituents may be further substituents, and preferably the above-mentioned alkyl group has halogen atoms as substituents to become trifluoromethyl or other haloalkyl groups.

[0466] The aforementioned substituents are preferably formed by any combination to create acid-degradable groups.

[0467] Furthermore, the term "acid-decomposing group" refers to a group that decomposes through the action of an acid to produce a polar group, preferably a group that is released by the action of an acid to protect the structure of the polar group. The aforementioned polar group and leaving group are as described above.

[0468] Next, the cation (ZaI-2) will be explained.

[0469] The cation (ZaI-2) is R in the formula (ZaI). 201 ~R 203 Each cation represents an organic group that does not have an aromatic ring. An aromatic ring also includes aromatic rings containing heteroatoms.

[0470] As R 201 ~R 203 The number of carbon atoms in the organic group that does not have an aromatic ring is preferably 1 to 30, more preferably 1 to 20.

[0471] As R 201 ~R 203 Each of the following is 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.

[0472] As R 201 ~R 203 Alkyl and cycloalkyl groups, for example, include straight-chain alkyl groups with 1 to 10 carbon atoms or branched alkyl groups with 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), and cycloalkyl groups with 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl).

[0473] R 201 ~R 203 It can be further substituted with halogen atoms, alkoxy groups (e.g., 1 to 5 carbon atoms), hydroxyl groups, cyano groups, or nitro groups.

[0474] R 201 ~R 203 The substituents are also preferably formed by any combination of substituents to form acid-degradable groups.

[0475] Next, the cation (ZaI-3b) will be explained.

[0476] The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0477] [Chemical Formula 18]

[0478]

[0479] In formula (ZaI-3b), R 1c ~R 5c Each can independently represent a hydrogen atom, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio, or arylthio.

[0480] R 6c and R 7c Each can be independently represented by a hydrogen atom, an alkyl group (e.g., tert-butyl), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

[0481] R x and R y Each can be independently represented as alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl, or vinyl.

[0482] R 1c ~R 7c and R x and R y The substituents are also preferably formed by any combination of substituents to form acid-degradable groups.

[0483] R 1c ~R 5c Any two or more of R 5c With R 6c R 6c With R 7c R 5c With R x and R x With R y They can bond with each other to form a ring, which can independently contain oxygen atoms, sulfur atoms, ketone groups, ester bonds or amide bonds.

[0484] Examples of the aforementioned rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of rings include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0485] As R 1c ~R 5c Any two or more of R 6c With R 7c and Rx With R y Examples of alkyl groups formed by bonding include butylene and pentylene. The methylene group in this alkyl group can be replaced by heteroatoms such as oxygen atoms.

[0486] As R 5c With R 6c and R 5c With R x The bonded group is preferably a single bond or an alkylene group. Examples of alkylene groups include methylene and ethylene.

[0487] R 1c ~R 5c R 6c R 7c R x R y and R 1c ~R 5c Any two or more of R 5c With R 6c R 6c With R 7c R 5c With R x and R x With R y The rings formed by bonding the individual components together can have substituents.

[0488] Next, the cation (ZaI-4b) will be explained.

[0489] The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0490] [Chemical Formula 19]

[0491]

[0492] In equation (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8.

[0493] R 13 This refers to 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 can be the cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have substituents.

[0494] R 14This indicates a hydroxyl group, a halogen atom (e.g., fluorine and iodine atoms), 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. R 14 When multiple groups are present, each group independently represents the aforementioned groups such as hydroxyl.

[0495] R 15 Each R can independently represent an alkyl, cycloalkyl, or naphthyl group. Two Rs 15 They can bond together to form a ring. Two Rs 15 When they bond together to form a ring, the ring framework can contain heteroatoms such as oxygen or nitrogen atoms.

[0496] In one approach, two Rs are preferred. 15 It is an alkylene group, and they are bonded together to form a cyclic structure. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, and the above-mentioned naphthyl group, as well as the two R groups... 15 The rings formed by mutual bonding can have substituents.

[0497] In equation (ZaI-4b), R 13 R 14 and R 15 The alkyl group can be straight-chain or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably methyl, ethyl, n-butyl, or tert-butyl, etc.

[0498] R 13 ~R 15 and R x and R y Each substituent is also preferably formed by any combination of substituents to form an acid-decomposable group.

[0499] The following shows M1 + The present invention is not limited to the specific examples of sulfonium cations represented herein.

[0500] [Chemical Formula 20]

[0501]

[0502] [Chemical Formula 21]

[0503]

[0504] [Chemical Formula 22]

[0505]

[0506] The photoacid generator can be a compound other than the compound represented by the above formula (T-1).

[0507] As a photoacid generator, for example, one can cite M + X - The compound indicated by "" (onium salt) is preferably a compound that produces an organic acid by exposure. Examples of 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 imide acids, bis(alkyl sulfonyl) imide acids, and tri(alkyl sulfonyl) methyl acids.

[0508] In the case of “M” + X - In the compounds represented by "", M + It represents a cation, preferably an organic cation.

[0509] There are no particular restrictions on whether a cation can be monovalent or divalent or higher.

[0510] As a cation, it is preferred to be a cation represented by the aforementioned formula (ZaI) or a cation represented by the following formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0511] [Chemical Formula 23]

[0512]

[0513] In formula (ZaII), R 204 and R 205 Each can be represented independently as aryl, alkyl, or cycloalkyl.

[0514] As R 204 and R 205 The aryl group is preferably phenyl or naphthyl, more preferably phenyl. 204 and R 205 The aryl group can be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of aryl groups with heterocycles include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0515] As R 204 and R 205 The alkyl and cycloalkyl groups are preferably straight-chain alkyl groups with 1 to 10 carbon atoms or branched alkyl groups with 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or cycloalkyl groups with 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0516] R 204 and R 205 The aryl, alkyl, and cycloalkyl groups can each independently have substituents. As R 204 and R205 The aryl, alkyl, and cycloalkyl groups may have substituents, for example, alkyl (e.g., 1-15 carbon atoms), cycloalkyl (e.g., 3-15 carbon atoms), aryl (e.g., 6-15 carbon atoms), alkoxy (e.g., 1-15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. Additionally, R... 204 and R 205 The substituents are also preferably formed by any combination of substituents to form acid-degradable groups.

[0517] In the case of “M” + X - In the compound represented by "X", - It represents an anion, preferably an organic anion.

[0518] There are no particular restrictions on what can be considered an anion; examples of monovalent or divalent anions can be given.

[0519] As an anion, it is preferably an anion with extremely low ability to induce nucleophilic reactions, and more preferably a non-nucleophilic anion.

[0520] 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.), sulfonamide anions, bis(alkylsulfonyl)imide anions, and tri(alkylsulfonyl)methyl anions.

[0521] 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.

[0522] The aforementioned alkyl group can be, for example, a fluoroalkyl group (which may have substituents other than fluorine atoms. It can also be a perfluoroalkyl group).

[0523] 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.

[0524] 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 atoms, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably 1 to 15 carbon atoms), alkyl (preferably 1 to 10 carbon atoms), cycloalkyl (preferably 3 to 15 carbon atoms), aryl (preferably 6 to 14 carbon atoms), alkoxycarbonyl (preferably 2 to 7 carbon atoms), acyl (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy (preferably 2 to 7 carbon atoms), alkylthio (preferably 1 to 15 carbon atoms), alkylsulfonyl (preferably 1 to 15 carbon atoms), alkyliminosulfonyl (preferably 1 to 15 carbon atoms), and aryloxysulfonyl (preferably 6 to 20 carbon atoms) are examples.

[0525] The aralkyl group in the aralkyl carboxylic acid anion is preferably an aralkyl group with 7 to 14 carbon atoms.

[0526] Examples of aralkyl groups having 7 to 14 carbon atoms include benzoyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl.

[0527] Examples of sulfonamide anions include, for instance, saccharin anion.

[0528] The alkyl group in the bis(alkylsulfonyl)imide anion and the tri(alkylsulfonyl)methyl anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred.

[0529] Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion can also bond with each other to form a ring structure. This increases the acid strength.

[0530] Other non-nucleophilic anions include, for example, phosphorus fluoride (e.g., PF6). - Boron fluoride (e.g., BF4) - ), and antimony fluoride (e.g., SbF6), and antimony fluoride (e.g - ).

[0531] As a non-nucleophilic anion, the preferred anion is an aliphatic sulfonic acid anion in which at least the α-position 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)imide anion in which the alkyl group is substituted with a fluorine atom, or a tri(alkylsulfonyl)methyl 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, it is a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, a pentafluorobenzenesulfonic acid anion, or a 3,5-bis(trifluoromethyl)benzenesulfonic acid anion.

[0532] As a non-nucleophilic anion, it is also preferred to be an anion represented by the following formula (AN1).

[0533] [Chemical Formula 24]

[0534]

[0535] In formula (AN1), R 1 and R 2 Each can be used to represent a hydrogen atom or a substituent independently.

[0536] There are no particular limitations on the substituents, but non-electron-withdrawing groups are preferred. Examples of non-electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups.

[0537] The non-electron-withdrawing groups are preferably -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR', respectively. R' is a monovalent hydrocarbon group.

[0538] Examples of monovalent hydrocarbon groups represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl, propynyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornyl; aryl groups such as phenyl, tolyl, xylyl, mesitylelel, naphthyl, methylnaphthyl, anthracenel, and methylanthrayl; and aralkyl groups such as benzoyl, phenethyl, phenylpropyl, naphthylmethyl, and anthracenemethyl.

[0539] Among them, R 1 and R 2 Each is preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom, independently.

[0540] L represents a divalent linker.

[0541] When there are multiple L, L can be the same or different.

[0542] Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene (preferably with 1 to 6 carbon atoms), cycloalkylene (preferably with 3 to 15 carbon atoms), alkenyl (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple of these. Among these, the preferred divalent linking groups are -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene-, -COO-alkylene-, or -CONH-alkylene-, more preferably -O-CO-O-, -O-CO-O-alkylene-, -COO-, -CONH-, -SO2-, or -COO-alkylene-.

[0543] As L, for example, it is preferably a group represented by the following formula (AN1-1).

[0544] * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0545] In formula (AN1-1), * a R in equation (AN1) 3 The bonding positions.

[0546] * b This represents -C(R) in equation (AN1). 1 (R) 2 The bonding position of )-.

[0547] X and Y each independently represent integers from 0 to 10, preferably integers from 0 to 3.

[0548] R 2a and R 2b Each can be used to represent a hydrogen atom or a substituent independently.

[0549] When R 2a and R 2b When there are multiple R values, there are multiple R values. 2a and R 2b They can be the same or different.

[0550] When Y is 1 or more, it is related to -C(R) in equation (AN1). 1 (R) 2 )- Directly bonded CR2b R in 2 2b It is a substance other than fluorine atoms.

[0551] Q represents * A -O-CO-O-﹡ B 、* A -CO-﹡ B 、* A -CO-O-﹡ B 、* A -O-CO-﹡ B 、* A -O-﹡ B 、* A -S-﹡ B ,or* A -SO2-* B .

[0552] Where X+Y in equation (AN1-1) is greater than or equal to 1 and R in equation (AN1-1) 2a and R 2b When all atoms are hydrogen atoms, Q represents *. A -O-CO-O-﹡ B 、* A -CO-﹡ B 、* A -O-CO-﹡ B 、* A -O-﹡ B 、* A -S-﹡ B ,or* A -SO2-* B .

[0553] * A R in expression (AN1) 3 Side bonding position, * B -SO3 in expression (AN1) - The bonding position on the side.

[0554] In formula (AN1), R 3 It represents an organic group.

[0555] 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. These organic groups may or may not have substituents. They may or may not have heteroatoms (oxygen, sulfur, and / or nitrogen atoms, etc.).

[0556] Among them, R 3Preferably, the organic group has a cyclic structure. The cyclic structure can be monocyclic or polycyclic, and may also have substituents. Preferably, the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN1).

[0557] Organic groups having the above-mentioned cyclic structure may or may not have heteroatoms (oxygen, sulfur, and / or nitrogen atoms, etc.). The heteroatoms may be substituted with one or more carbon atoms forming the cyclic structure.

[0558] The organic groups having the above-mentioned cyclic structure are preferably, for example, cyclic hydrocarbon groups, lactone cyclic groups, and sulfonyl lactone cyclic groups. Among them, the organic groups having the above-mentioned cyclic structure are preferably cyclic hydrocarbon groups.

[0559] The hydrocarbon group in the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents.

[0560] The aforementioned cycloalkyl group can be monocyclic (cyclohexyl, etc.) or polycyclic (adamantyl, etc.), and the number of carbon atoms is preferably 5 to 12.

[0561] As the aforementioned lactone group and sulfonolactone group, for example, it is preferably a group formed by removing a hydrogen atom from the cyclic atom constituting the lactone structure or sulfonolactone structure in any of the structures represented by the aforementioned formulas (LC1-1) to (LC1-22) and the structures represented by formulas (SL1-1) to (SL1-3).

[0562] R 3 Preferably, it contains halogen atoms. As R 3 The halogen atoms contained therein are preferably fluorine atoms or iodine atoms, more preferably iodine atoms. When the resist composition is used as an EUV resist, the more halogen atoms the better from the viewpoint of EUV light absorption efficiency. When iodine atoms are present, a structure directly bonded to carbon atoms on an aromatic ring is preferred.

[0563] The anion represented by formula (AN1) is preferably the anion described in

[0040] to

[0044] of Japanese Patent Application Publication No. 2018-155908.

[0564] As a non-nucleophilic anion, it can be a benzenesulfonic acid anion, preferably a benzenesulfonic acid anion substituted with branched alkyl or cycloalkyl groups.

[0565] As a non-nucleophilic anion, it is also preferred to be an anion represented by the following formula (AN2).

[0566] [Chemical Formula 25]

[0567]

[0568] 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.

[0569] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group without a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. As for the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred.

[0570] 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 fluorine atoms as Xf.

[0571] R 4 and R 5 Each of these can independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When R... 4 and R 5 When multiple exist, R 4 and R 5 They can be the same or different.

[0572] By R 4 and R 5 The alkyl group represented is preferably composed of 1 to 4 carbon atoms. The alkyl group may have substituents. Hydrogen atoms are preferred as R4 and R5.

[0573] L represents a divalent linker. The definition of L is synonymous with L in formula (AN1).

[0574] W represents an organic group containing a cyclic structure. Preferably, it is a cyclic organic group.

[0575] Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups.

[0576] The alicyclic group can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among these, alicyclic groups with a large volumetric structure, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl, are preferred.

[0577] The aryl group can be monocyclic or polycyclic. Examples of the aforementioned aryl groups include phenyl, naphthyl, phenanthryl, and anthracene.

[0578] The heterocyclic group can be monocyclic or polycyclic. When it is a polycyclic heterocyclic group, it can further suppress acid diffusion. The heterocyclic group can be aromatic or non-aromatic. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocycles include tetrahydropyran rings, lactone rings, sulfonyl lactone rings, and decahydroisoquinoline rings. The preferred heterocycles in the heterocyclic group are furan rings, thiophene rings, pyridine rings, or decahydroisoquinoline rings.

[0579] The aforementioned cyclic organic groups may have substituents. Examples of such substituents include alkyl groups (which may be either straight-chain 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 constituting the cyclic organic group (the carbon that facilitates ring formation) may also be a carbonyl carbon.

[0580] The preferred anion, represented by formula (AN2), is 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) q -W, or SO3 - -CF2-CH(CF3)-OCO-(L) q' -W. Here, L, q, and W are the same as in equation (AN2). q' represents an integer from 0 to 10.

[0581] W preferably contains halogen atoms. The halogen atoms contained in W are preferably fluorine or iodine atoms, more preferably iodine atoms. When the resist composition is used as an EUV resist, the more halogen atoms the better from the viewpoint of EUV light absorption efficiency. When iodine atoms are present, a structure directly bonded to carbon atoms on an aromatic ring is preferred.

[0582] The anion represented by formula (AN2) is preferably the anion described in International Publication No. 2023 / 157455

[0076] , Japanese Patent Application Publication No. 2021-81708

[0071] to

[0089] , Japanese Patent Application Publication No. 2018-5224

[0033] to

[0045] , and Japanese Patent Application Publication No. 2018-25789

[0031] to

[0039] .

[0583] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0584] [Chemical Formula 26]

[0585]

[0586] 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 are fluorine atoms and hydroxyl groups.

[0587] 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.

[0588] D represents a single bond or a divalent linking group. Examples of divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate groups, ester groups, and groups consisting of two or more of these.

[0589] B represents a hydrocarbon group.

[0590] 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.

[0591] B preferably contains halogen atoms. The halogen atom contained in B is preferably a fluorine atom or an iodine atom, more preferably an iodine atom. When the resist composition is used as an EUV resist, the more halogen atoms the better from the viewpoint of EUV light absorption efficiency. When iodine atoms are present, a structure directly bonded to a carbon atom on an aromatic ring is preferred.

[0592] The anion represented by formula (AN3) is preferably the anion described in Japanese Patent Application Publication No. 2018-159744

[0029] to

[0034] and Japanese Patent Application Publication No. 2018-155908

[0045] .

[0593] As a non-nucleophilic anion, disulfonamide anion is also preferred.

[0594] Disulfonamide anion, for example, is composed of N... -(SO2-R q )2 represents anion.

[0595] Here, R q This indicates an alkyl group that may have substituents, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. Two Rs q They can bond together to form a ring. Two Rs q The groups formed by mutual bonding are preferably alkylene groups that can have substituents, preferably fluoroalkylene groups, and more preferably perfluoroalkylene groups. The number of carbon atoms in the above-mentioned alkylene groups is preferably 2 to 4.

[0596] In addition, non-nucleophilic anions can also be represented by the following formulas (d1-1) to (d1-4).

[0597] [Chemical Formula 27]

[0598]

[0599] In equation (d1-1), R 51 This indicates a hydrocarbon group (e.g., aryl, such as phenyl) that may have substituents (e.g., hydroxyl).

[0600] In equation (d1-2), Z 2c This indicates 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).

[0601] Z 2c The hydrocarbon group described above can be linear, branched, or have a cyclic structure. Furthermore, the carbon atom in the hydrocarbon group (preferably the carbon atom that forms the ring 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.

[0602] In equation (d1-2), “Z” 2c -SO3 - "Preferably, it is different from the anion represented by the aforementioned formulas (AN1) to (AN3). For example, Z..." 2c Preferably, it is a substance other than an aryl group. For example, Z 2c In, relative to -SO3 - The atoms at the α and β positions are preferably atoms other than carbon atoms having fluorine atoms as substituents. For example, Z 2c relative to -SO3 - The atom at the α-position and / or the atom at the β-position are preferably cyclic atoms in the cyclic group.

[0603] In equation (d1-3), R 52Y represents an organic group (preferably a hydrocarbon group with a fluorine atom). 3 Rf indicates a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf indicates a hydrocarbon group.

[0604] In equation (d1-4), R 53 and R 54 Each organic group (preferably a hydrocarbon group having a fluorine atom) is represented independently. R 53 With R 54 They can bond together to form a ring.

[0605] Organic anions can be used alone or in combination with two or more.

[0606] The photoacid generator can be at least one selected from the group consisting of compounds (I) to (II).

[0607] (Compound (I))

[0608] Compound (I) 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 that produces an acid by irradiation with photochemical rays or radiation, comprising 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.

[0609] Structural site X: composed of anion site A1 - and cation site M 11 + The structural part that constitutes and forms the first acidic region represented by HA1 through irradiation by photochemical rays or radiation.

[0610] Structural region Y: composed of anion site A2 - and cation site M 12 + The structural part that constitutes and forms the second acidic region represented by HA2 through irradiation by photochemical rays or radiation.

[0611] The above compound (I) satisfies the following condition I.

[0612] Condition I: In the above compound (I), the above-mentioned cation site M in the above-mentioned structural site X is... 11 + and the aforementioned cation site M in the aforementioned structural site Y. 12 + Replace with H + The resulting compound PI has a cation site M derived from the above-mentioned structural site X. 11 + Replace with H +The acid dissociation constant a1 of the acidic site represented by HA1 and the cation site M derived from the above structural site Y. 12 + Replace with H + The acid dissociation constant a2 of the acidic site represented by HA2 is obtained, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0613] The following is a more detailed explanation of condition I.

[0614] When compound (I) is, for example, a compound that produces 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".

[0615] The acid dissociation constants a1 and a2 of compound PI, more specifically, refer to the acid dissociation constants a1 and a2 of compound PI. More specifically, given the acid dissociation constants of compound PI, compound PI is considered to have "a1 acid dissociation constant". - When the compound with HA2 is given by pKa, the acid dissociation constant a1 is given. The above-mentioned compound with A1... - Compounds containing HA2" become "compounds with A1 - and A2 - The pKa of the compound is the acid dissociation constant a2.

[0616] When compound (I) is, for example, a compound that produces an acid having two first acidic sites derived from the above-described structural site X and one second acidic site derived from the above-described structural site Y, compound PI is equivalent to "a compound having two HA1 and one HA2".

[0617] Having determined the acid dissociation constant of compound PI, compound PI becomes "having an A1 - The acid dissociation constant of a compound with one HA1 and one HA2 and the acid dissociation constant of a compound with one HA1 and one HA2 are as follows: - A compound with one HA1 and one HA2 is called a compound with two A1s. - The acid dissociation constant of a compound containing HA2 is equivalent to the aforementioned acid dissociation constant a1. "Having two A1s..." - A compound with one HA2 becomes a compound with two A1s. - and A2 - The acid dissociation constant of the compound is equivalent to the acid dissociation constant a2. That is, in the case of compound PI, the cation M derived from the above-mentioned structural site X is... 11 + Replace with H +When multiple acid dissociation constants exist for the acidic site represented by HA1, the value of acid dissociation constant a2 is greater than the maximum value among the multiple acid dissociation constants a1. Furthermore, compound PI is termed "having one A1". - Let the acid dissociation constant of a compound having one HA1 and one HA2 be aa, and let the acid dissociation constant of a compound having one HA1 be aa. - A compound with one HA1 and one HA2 is called a compound with two A1s. - When the acid dissociation constant of a compound with HA2 is set as ab, the relationship between aa and ab satisfies aa <ab。

[0618] The acid dissociation constants a1 and a2 can be determined using the aforementioned method for determining the acid dissociation constant.

[0619] The aforementioned compound PI is equivalent to the acid produced when compound (I) is irradiated with photochemical rays or radiation.

[0620] When compound (I) has two or more structural sites X, the structural sites X can be the same or different. Furthermore, two or more of the above-mentioned A1... - and two or more of the above M 11 + They can be the same or different.

[0621] In compound (I), the above A1 - Compared with A2 above - and the aforementioned M 11 + With the above M 12 + They can be the same or different, but the above A1 - Compared with A2 above - The preferred options are different.

[0622] In the aforementioned compound PI, the absolute value of the difference between the acid dissociation constant a1 (or its maximum value when multiple acid dissociation constants a1 exist) 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 limitation on the upper limit of the absolute value of the difference between the acid dissociation constant a1 (or its maximum value when multiple acid dissociation constants a1 exist) and the acid dissociation constant a2; for example, it may be 16 or less.

[0623] In the above-mentioned compound PI, the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less. Furthermore, as a lower limit value of the acid dissociation constant a2, it is preferably -4.0 or more.

[0624] In the above-mentioned compound PI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less. Furthermore, as a lower limit value of the acid dissociation constant a1, it is preferably -20.0 or more.

[0625] Anion site A1 - and anion site A2 - The structural site is a negatively charged atom or group 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.

[0626] As the anion site A1 - Preferably, it is an anionic site that can form an acidic site with a small acid dissociation constant, more preferably any one of formulas (AA-1) to (AA-3), and even more preferably any one of formulas (AA-1) and (AA-3).

[0627] In addition, A2 is the anion site. - Preferably, it can form an acid dissociation constant with a higher acid dissociation constant than the anion site A1. - The anionic site of the large acidic site is more preferably any one of formulas (BB-1) to (BB-6), and even more preferably any one of formulas (BB-1) and (BB-4).

[0628] Furthermore, in the following equations (AA-1) to (AA-3) and (BB-1) to (BB-6), * represents the bonding position.

[0629] In equation (AA-2), R A Represents a monovalent organic group. Derived by R A There are no particular limitations on the monovalent organic group represented; for example, cyano, trifluoromethyl, and methanesulfonyl groups can be cited.

[0630] [Chemical Formula 28]

[0631]

[0632] [Chemical Formula 29]

[0633]

[0634] Cation site M 11 + and cation site M 12 + For structural sites containing positively charged atoms or groups of atoms, examples include monovalent organic cations. Furthermore, examples of organic cations include those derived from the aforementioned M... + The organic cation represented.

[0635] (Compound (II))

[0636] Compound (II) is a compound having two or more of the above-described structural sites X and one or more of the above-described structural sites Z, and is a compound that produces an acid containing two or more of the above-described 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.

[0637] Structural site Z: Nonionic site capable of neutralizing acids

[0638] In compound (II), the definition of structural site X and A1 - and M 11 + The definition is the same as the definition of structural site X in the aforementioned compound (I), and A1 - and M 11 + The definitions are synonymous, and the preferred selection methods are also the same.

[0639] In the above compound (II), the above-mentioned cation site M in the above-mentioned structural site X is... 11 + Replace with H + In the compound PII formed, the cation M derived from the above-mentioned structural site X is derived from the above-mentioned structural site X. 11 + Replace with H + The preferred range of the acid dissociation constant a1 of the acidic site represented by HA1 is the same as the preferred range of the acid dissociation constant a1 in the above-mentioned compound PI.

[0640] Furthermore, when compound (II) is, for example, a compound that produces an acid having two acidic sites derived from the first acidic site X and the acidic site Z, compound PII is equivalent to "a compound having two HA1s". After determining the acid dissociation constant of compound PII, compound PII becomes "a compound having one A1". - The acid dissociation constant of a compound with an HA1 and the acid dissociation constant of a compound with an A1 - A compound with one HA1 becomes a compound with two A1s. - The acid dissociation constant of the compound is equivalent to the acid dissociation constant a1.

[0641] The acid dissociation constant a1 can be determined using the aforementioned method for determining the acid dissociation constant.

[0642] The above compound PII is equivalent to the acid produced when compound (II) is irradiated with photochemical rays or radiation.

[0643] Furthermore, the two or more structural parts X mentioned above can be the same or different. The two or more of the above A1- and two or more of the above M 11 + They can be the same or different.

[0644] There are no particular limitations on the nonionicity of the site that can neutralize the acid in structural site Z. For example, sites containing groups that can electrostatically interact with protons or functional groups with electrons are preferred.

[0645] As functional groups capable of electrostatic interaction with protons or possessing electrons, examples include functional groups with macrocyclic structures such as cyclic polyethers, or functional groups with nitrogen atoms that have non-shared electron pairs that do not contribute to π-conjugation. Nitrogen atoms with non-shared electron pairs that do not contribute to π-conjugation refer to nitrogen atoms having, for example, a partial structure as shown in the following formula.

[0646] [Chemical Formula 30]

[0647]

[0648] Examples of structures that are functional groups capable of electrostatically interacting with protons include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, with primary to tertiary amine structures being preferred.

[0649] Examples of sites other than cations that compounds (I) and (II) may have are given.

[0650] [Chemical Formula 31]

[0651]

[0652] [Chemical Formula 32]

[0653]

[0654] Photoacid generators can be intramolecular salts.

[0655] The content of the photoacid generating agent in the photoresist composition is not particularly limited, but it is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5.0% by mass or more, relative to the total solid content of the photoresist composition. Furthermore, the content of the photoacid generating agent is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the photoresist composition.

[0656] The photoacid generator may be a single agent or two or more agents. When two or more photoacid generators are used, it is preferable that their total content is within the above-mentioned preferred content range.

[0657] When the photoresist composition contains a compound comprising a sulfonium cation and an anion having an iodine atom as a photoacid generator, the content of the compound comprising the sulfonium cation and the anion having an iodine atom relative to the total amount of photoacid generator in the photoresist composition is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, and even more preferably 50 to 100% by mass.

[0658] When the resist composition contains a compound comprising a sulfonium cation and an anion having an iodine atom as a photoacid generator, only one of the compounds comprising the sulfonium cation and the anion having an iodine atom may be used, or two or more compounds may be used. When two or more compounds are used, it is preferable that their total content is within the preferred content range described above.

[0659] [Acid diffusion control agent]

[0660] The resist composition contains an acid diffusion control agent.

[0661] The acid diffusion control agent can function as a quencher, which captures, for example, the acid generated from the photoacid generator during exposure and inhibits the reaction of the resin (A) in the unexposed part caused by excess generated acid.

[0662] The acid diffusion control agent is preferably a carboxylate.

[0663] The acid diffusion control agent is preferably selected from at least one of the group consisting of compounds represented by the following formula (S-1) and compounds represented by the following formula (S-2).

[0664] [Chemical Formula 33]

[0665]

[0666] In equation (S-1),

[0667] R S1 It represents a hydrogen atom or a substituent.

[0668] L S1 Indicates a single bond or a linking group.

[0669] X S1 Indicates a single bond or a linking group.

[0670] M2 + It represents a sulfonium cation.

[0671] Among them, R S1 L S1 and X S1 At least one of them contains an iodine atom.

[0672] In equation (S-2),

[0673] RS2 and R S3 Each can be used to represent a hydrogen atom or a substituent independently.

[0674] L S2 and L S3 Each can be used independently to represent a single bond or a linking group.

[0675] M3 + It represents a sulfonium cation.

[0676] Among them, R S2 R S3 L S2 and L S3 At least one of them contains an iodine atom.

[0677] L in equation (S-1) S1 Indicates a single bond or a linking group.

[0678] L S1 The linking group is not particularly limited, and examples include -O-, -S-, -CO-, -O-CO-, -O-CO-O-, -SO-, -SO2-, -SO-, -NQ-, -NQ-CO-, -CO-NQ-CO-, -NQ-SO2-, alkylene, cycloalkylene, arylene, heteroarylene, and groups formed by combining two or more of these. Q represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group (preferably with 1 to 10 carbon atoms), a cycloalkyl group (preferably with 3 to 15 carbon atoms), or an aryl group (preferably with 6 to 15 carbon atoms). Q can be connected with R. S1 or X S1 They bond together to form a ring.

[0679] As L S1 The alkylene group represented is not particularly limited, but is preferably an alkylene group with 1 to 10 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene, and more preferably an alkylene group with 1 to 6 carbon atoms. S1 The alkylene group represented may have substituents.

[0680] L S1 The number of carbon atoms in the represented cycloalkyl group is not particularly limited; for example, it is preferably 3 to 20, more preferably 4 to 15. The cycloalkyl group can be a monocyclic cycloalkyl group such as cyclopentylene or cyclohexylene, or a polycyclic cycloalkyl group such as norbornylene, tetracyclodecylene, tetracyclododecylene, or adamantylene. One or more methylene groups in the cycloalkane ring constituting the cycloalkyl group can be substituted with heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, or ester bonds, or with vinylene groups. Furthermore, one or more ethylene groups in the cycloalkane ring constituting the cycloalkyl group can be substituted with vinylene groups. S1The cycloalkylene groups represented may have substituents.

[0681] As L S1 The arylene group represented is not particularly limited; for example, arylene groups with 6 to 20 carbon atoms can be cited, with arylene groups with 6 to 15 carbon atoms being preferred. As an arylene group, phenylene or naphthylene is preferred, with phenylene being particularly preferred. S1 The arylene group represented may have substituents.

[0682] As L S1 The heteroaryl group represented is not particularly limited; for example, it is preferably a heteroaryl group with 3 to 19 carbon atoms, and more preferably a heteroaryl group with 4 to 14 carbon atoms. The heteroaryl group preferably includes at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as the cyclic atom. S1 The number of cyclic atoms in the represented heteroaryl group is preferably 4 to 20, more preferably 5 to 15. S1 The heteroaryl group represented may have substituents.

[0683] X in equation (S-1) S1 Indicates a single bond or a linking group.

[0684] As X S1 The linking group represented is not particularly limited; examples include -O-, -S-, -CO-, -O-CO-, -O-CO-O-, -SO-, -SO2-, -SO-, and -NQ. 1 -、-NQ 1 -CO-、-CO-NQ 1 -CO-、-NQ 1 -SO2-, alkylene, cycloalkylene, aryl, heteroaryl, and groups formed by combining two or more of these. Q 1 The symbol represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group (preferably with 1 to 10 carbon atoms), a cycloalkyl group (preferably with 3 to 15 carbon atoms), or an aryl group (preferably with 6 to 15 carbon atoms). Q 1 Can be used with R S1 or L S1 They bond together to form a ring.

[0685] As X S1 The alkylene group represented is not particularly limited, but is preferably an alkylene group with 1 to 10 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene, and more preferably an alkylene group with 1 to 6 carbon atoms.

[0686] X S1The alkylene group may have substituents. Substituents are not particularly limited; for example, the substituent T mentioned above is preferred, such as hydroxyl, halogen atom, cycloalkyl, aryl, etc.

[0687] X S1 The number of carbon atoms in the represented cycloalkyl group is not particularly limited; for example, it is preferably 3 to 20, more preferably 4 to 15. The cycloalkyl group can be a monocyclic cycloalkyl group such as cyclopentylene or cyclohexylene, or a polycyclic cycloalkyl group such as norbornylene, tetracyclodecylene, tetracyclododecylene, or adamantylene. One or more methylene groups in the cycloalkane ring constituting the cycloalkyl group can be substituted with heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, or ester bonds, or with vinylene groups. Furthermore, one or more ethylene groups in the cycloalkane ring constituting the cycloalkyl group can be substituted with vinylene groups.

[0688] X S1 The cycloalkylene group represented may have substituents. Substituents are not particularly limited; for example, the substituent T mentioned above is preferred, such as hydroxyl, halogen atom, cycloalkyl, aryl, etc.

[0689] As X S1 The arylene group represented is not particularly limited; for example, arylene groups with 6 to 20 carbon atoms can be cited, and arylene groups with 6 to 15 carbon atoms are preferred. As an arylene group, phenylene or naphthylene is preferred, and phenylene is particularly preferred.

[0690] X S1 The arylene group represented may have substituents. Substituents are not particularly limited; for example, the substituent T mentioned above is preferred, such as hydroxyl, halogen atom, cycloalkyl, aryl, etc.

[0691] As X S1 The heteroaryl group represented is not particularly limited; for example, it is preferably a heteroaryl group with 3 to 19 carbon atoms, and more preferably a heteroaryl group with 4 to 14 carbon atoms. The heteroaryl group preferably includes at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a cyclic atom. S1 The number of cyclic atoms of the heteroaryl group represented is preferably 4 to 20, more preferably 5 to 15.

[0692] X S1 The heteroaryl group represented may have substituents. Substituents are not particularly limited; for example, the substituent T mentioned above is preferred, such as hydroxyl, halogen atom, cycloalkyl, aryl, etc.

[0693] R in equation (S-1) S1 It represents a hydrogen atom or a substituent.

[0694] R S1The substituents represented are not particularly limited. For example, the above-mentioned substituent T can be cited, preferably halogen atoms, alkyl, alkoxy, alkylthio, cycloalkyl, cycloalkoxy, cycloalkylthio, aryl, heteroaryl, aryloxy, arylthio, etc.

[0695] R S1 The halogen atom represented is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or an iodine atom, and even more preferably an iodine atom.

[0696] R S1 The alkyl group can be either straight-chain or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have substituents. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and trifluoromethyl.

[0697] Regarding R S1 The description, specific examples, and preferred range of the alkyl groups included in the alkoxy and alkathioyl groups represented are consistent with those of the above-mentioned R. S1 The alkyl groups represented are the same.

[0698] R S1 The cycloalkyl group can be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, more preferably 4 to 15. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. The cycloalkyl group may have substituents. One or more methylene groups in the cycloalkane ring constituting the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, ester bonds, or vinylidenes. Furthermore, one or more ethylides constituting the cycloalkane ring in the cycloalkyl group may be substituted with vinylides.

[0699] Regarding R S1 The description, specific examples, and preferred range of the cycloalkyl groups contained in the cycloalkoxy and cycloalkylthio groups represented are consistent with those of the above-mentioned R. S1 The cycloalkyl groups represented are the same.

[0700] R S1 The aryl group represented is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, further preferably phenyl or naphthyl, and particularly preferably phenyl. The aryl group may have substituents.

[0701] Regarding R S1 The description, specific examples, and preferred range of the aryl groups contained in the aryloxy and arylthyl groups represented are consistent with those of the above-mentioned R. S1 The aryl groups represented are the same.

[0702] R S1The heteroaryl group represented is preferably a heteroaryl group with 3 to 19 carbon atoms, more preferably a heteroaryl group with 4 to 14 carbon atoms. The heteroaryl group preferably includes at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a cyclic atom. S1 The heteroaryl group represented preferably has 4 to 20 cyclic atoms, more preferably 5 to 15. Examples of heteroaryl groups include pyrrole, furanyl, thiophene, indolyl, benzofuranyl, and benzothiophene. The heteroaryl group may have substituents.

[0703] Wherein, R in equation (S-1) S1 L S1 and X S1 At least one of them contains an iodine atom. R S1 L S1 and X S1 The total number of iodine atoms contained is one or more, preferably two or more.

[0704] R is preferred S1 and X S1 At least one of them contains an iodine atom, more preferably R. S1 Contains iodine atoms. As R S1 Examples of ways that include iodine atoms include R. S1 The way iodine atoms are represented and R S1 The substituents represented (e.g., alkyl, alkoxy, alkylthio, cycloalkyl, cycloalkoxy, cycloalkylthio, aryl, heteroaryl, aryloxy, arylthio, etc.) have iodine atoms in a manner that...

[0705] M2 in equation (S-1) + It represents a sulfonium cation.

[0706] M2 + The description, specific examples, and preferred range of the sulfonium cation are the same as those in formula (T-1) above. + same.

[0707] The compounds represented by formula (S-1) are preferably those described in International Publication No. 2023 / 157455

[0118] ,

[0144] , Japanese Patent Application Publication No. 2018-155902

[0026] to

[0028] , and Japanese Patent Application Publication No. 2023-108593

[0147] .

[0708] L in equation (S-2) S2 and L S3 Each can be used independently to represent a single bond or a linking group.

[0709] L S2 and L S3The linking group represented is not particularly limited, and examples include -O-, -S-, -CO-, -O-CO-, -O-CO-O-, -SO-, -SO2-, -SO-, and -NQ. 2 -、-NQ 2 -CO-、-CO-NQ 2 -CO-、-NQ 2 -SO2-, alkylene, cycloalkylene, aryl, heteroaryl, and groups formed by combining two or more of these. Q 2 The symbol represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group (preferably with 1 to 10 carbon atoms), a cycloalkyl group (preferably with 3 to 15 carbon atoms), or an aryl group (preferably with 6 to 15 carbon atoms). 2 Can be used with R S2 or R S3 They bond together to form a ring.

[0710] As L S2 and L S3 The alkylene group represented is not particularly limited, but is preferably a alkylene group with 1 to 10 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene, and more preferably a alkylene group with 1 to 6 carbon atoms. S2 and L S3 The alkylene group represented may have substituents.

[0711] L S2 and L S3 The number of carbon atoms in the represented cycloalkyl group is not particularly limited; for example, it is preferably 3 to 20, more preferably 4 to 15. The cycloalkyl group can be a monocyclic cycloalkyl group such as cyclopentylene or cyclohexylene, or a polycyclic cycloalkyl group such as norbornylene, tetracyclodecylene, tetracyclododecylene, or adamantylene. One or more methylene groups in the cycloalkane ring constituting the cycloalkyl group can be substituted with heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, or ester bonds, or with vinylene groups. Furthermore, one or more ethylene groups in the cycloalkane ring constituting the cycloalkyl group can be substituted with vinylene groups. S2 and L S3 The cycloalkylene groups represented may have substituents.

[0712] As L S2 and L S3 The arylene group represented is not particularly limited; for example, arylene groups with 6 to 20 carbon atoms can be cited, with arylene groups with 6 to 15 carbon atoms being preferred. As an arylene group, phenylene or naphthylene is preferred, with phenylene being particularly preferred. S2 and L S3 The arylene group represented may have substituents.

[0713] As LS2 and L S3 The heteroaryl group represented is not particularly limited; for example, it is preferably a heteroaryl group with 3 to 19 carbon atoms, and more preferably a heteroaryl group with 4 to 14 carbon atoms. The heteroaryl group preferably includes at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as the cyclic atom. S2 and L S3 The number of cyclic atoms in the represented heteroaryl group is preferably 4 to 20, more preferably 5 to 15. S2 and L S3 The heteroaryl group represented may have substituents.

[0714] R in equation (S-2) S2 and R S3 Each can be used to represent a hydrogen atom or a substituent independently.

[0715] R S2 and R S3 The substituents represented are not particularly limited. For example, the above-mentioned substituent T can be cited, preferably halogen atoms, alkyl, alkoxy, alkylthio, cycloalkyl, cycloalkoxy, cycloalkylthio, aryl, heteroaryl, aryloxy, arylthio, etc.

[0716] R S2 and R S3 The halogen atom represented is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or an iodine atom, and even more preferably an iodine atom.

[0717] R S2 and R S3 The alkyl group can be either straight-chain or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have substituents. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and trifluoromethyl.

[0718] Regarding R S2 and R S3 The description, specific examples, and preferred range of the alkyl groups included in the alkoxy and alkathioyl groups represented are consistent with those of the above-mentioned R. S2 and R S3 The alkyl groups represented are the same.

[0719] R S2 and R S3The cycloalkyl group can be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, more preferably 4 to 15. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. The cycloalkyl group may have substituents. One or more methylene groups in the cycloalkane ring constituting the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms, carbonyl groups, sulfonyl groups, ester bonds, or vinylidenes. Furthermore, one or more ethylides constituting the cycloalkane ring in the cycloalkyl group may be substituted with vinylides.

[0720] Regarding R S2 and R S3 The description, specific examples, and preferred range of the cycloalkyl groups contained in the cycloalkoxy and cycloalkylthio groups represented are consistent with those of the above-mentioned R. S2 and R S3 The cycloalkyl groups represented are the same.

[0721] R S2 and R S3 The aryl group represented is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, further preferably phenyl or naphthyl, and particularly preferably phenyl. The aryl group may have substituents.

[0722] Regarding R S2 and R S3 The description, specific examples, and preferred range of the aryl groups contained in the aryloxy and arylthyl groups represented are consistent with those of the above-mentioned R. S2 and R S3 The aryl groups represented are the same.

[0723] R S2 and R S3 The heteroaryl group represented is preferably a heteroaryl group with 3 to 19 carbon atoms, more preferably a heteroaryl group with 4 to 14 carbon atoms. The heteroaryl group preferably includes at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms as a cyclic atom. S2 and R S3 The heteroaryl group represented preferably has 4 to 20 cyclic atoms, more preferably 5 to 15. Examples of heteroaryl groups include pyrrole, furanyl, thiophene, indolyl, benzofuranyl, and benzothiophene. The heteroaryl group may have substituents.

[0724] Wherein, R in equation (S-2) S2 R S3 L S2 and L S3 At least one of them contains an iodine atom. R S2 R S3 L S2 and L S3The total number of iodine atoms contained is one or more, preferably two or more.

[0725] R is preferred S2 and R S3 At least one of them contains an iodine atom. As R S2 and R S3 Examples of ways that include iodine atoms include R. S2 and R S3 The way iodine atoms are represented and R S2 and R S3 The substituents represented (e.g., alkyl, alkoxy, alkylthio, cycloalkyl, cycloalkoxy, cycloalkylthio, aryl, heteroaryl, aryloxy, arylthio, etc.) have iodine atoms in a manner that...

[0726] M3 in equation (S-2) + It represents a sulfonium cation.

[0727] M3 + The description, specific examples, and preferred range of the sulfonium cation are the same as those in formula (T-1) above. + same.

[0728] The compound represented by formula (S-2) is preferably the compound described in

[0039] to

[0047] of Japanese Patent Application Publication No. 2021-128331.

[0729] The acid diffusion control agent is a compound other than the compound represented by the above formula (S-1), and may be a compound other than the compound represented by the above formula (S-2).

[0730] There are no particular limitations on the types of acid diffusion control agents. Examples include basic compounds (DA), low molecular weight compounds (DB) with nitrogen atoms and groups that can be removed by the action of acid, and compounds (DC) whose acid diffusion control ability is reduced or lost by irradiation with photochemical rays or radiation.

[0731] Examples of compounds (DC) include onium salt compounds (DD) that are relatively weak acids relative to acids produced from photoacid generators, and basic compounds (DE) whose basicity decreases or disappears upon exposure to photochemical rays or radiation.

[0732] (Basic compound (DA))

[0733] As a basic compound (DA), it is preferred to be a compound having a structure represented by the following formulas (A) to (E).

[0734] [Chemical Formula 34]

[0735]

[0736] In equations (A) and (E),

[0737] R 200 R 201 and R 202 They can be the same or different, and each can independently represent a hydrogen atom, an alkyl group (preferably with 1 to 20 carbon atoms), a cycloalkyl group (preferably with 3 to 20 carbon atoms), or an aryl group (with 6 to 20 carbon atoms). R 200 R 201 and R 202 At least two of them can bond together to form a ring.

[0738] R 203 R 204 R 205 and R 206 They can be the same or different, and each can independently represent an alkyl group with 1 to 20 carbon atoms.

[0739] In equations (B), (C), (D), and (E), * represents the bonding position.

[0740] R in equations (A) and (E) 200 R 201 R 202 R 203 R 204 R 205 and R 206 The alkyl or cycloalkyl groups represented may have substituents or may be unsubstituted.

[0741] Regarding the aforementioned alkyl group, the preferred alkyl group having a substituent is an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.

[0742] R in equations (A) and (E) 200 R 201 R 202 R 203 R 204 R 205 and R 206 The alkyl or cycloalkyl groups represented are more preferably unsubstituted.

[0743] Examples of basic compounds (DA) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine.

[0744] Basic compounds (DA) can be compounds having at least one structure selected from the group consisting of imidazole, diazabicyclic, ononium hydroxide, ononium carboxylate, trialkylamine, aniline, and pyridine.

[0745] The basic compound (DA) can be an alkylamine derivative having at least one of the group consisting of a hydroxyl group and an ether bond, or an aniline derivative having at least one of the group consisting of a hydroxyl group and an ether bond, etc.

[0746] The difference between the pKa of the conjugate acid of the basic compound (DA) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the conjugate acid of the basic compound (DA)) is preferably 1.00 or more, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00.

[0747] Furthermore, the pKa of the conjugate acid of the basic compound (DA) varies depending on the type of photoacid generator used, for example, preferably 1.00 to 14.00, more preferably 3.00 to 13.00, and even more preferably 3.50 to 12.50.

[0748] (Onium salts (DDs) of acids that are relatively weak acids relative to the acids produced from photoacid generators)

[0749] Compounds (DD) can be compounds that produce acids when exposed to photochemical rays or radiation.

[0750] The compound (DD) is preferably a compound that produces an acid whose pKa is 1.00 or more greater than that of the acid produced from the photoacid generator.

[0751] The difference between the pKa of the acid produced from the compound (DD) and the pKa of the acid produced from the photoacid generator (the value obtained by subtracting the pKa of the acid produced from the photoacid generator from the pKa of the acid produced from the compound (DD)) is preferably 1.00 or more, more preferably 1.00 to 10.00, even more preferably 1.00 to 5.00, and particularly preferably 1.00 to 3.00.

[0752] Furthermore, the pKa of the acid generated from the compound (DD) varies depending on the type of photoacid generator used, and is preferably 0.50 to 10.00, more preferably 0.80 to 5.00, and even more preferably 1.00 to 5.00.

[0753] The compound (DD) is preferably an onium salt compound consisting of anion and cation.

[0754] As compounds (DD), for example, those composed of "M" can be cited. + X - " indicates a compound (onium salt). M" + X represents a cation. - Indicates anion. As M +Preferably, it is an organic cation, and examples include M as described in the description of the photoacid generator. + The same organic cation. As X - Organic anions are preferred. For example, anions represented by formulas (d1-1) to (d1-4) as described in the instructions for photoacid generators can be cited. Anions represented by formula (d1-1) or formula (d1-2) are preferred.

[0755] Specific examples of basic compounds (DA) include, for example, the compounds described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (DE) whose basicity is reduced or eliminated by irradiation with photochemical rays or radiation include the compounds described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824 and the compounds described in paragraph

[0164] of International Publication No. 2020 / 066824; specific examples of low molecular weight compounds (DB) having a nitrogen atom and a group that is removed by the action of an acid include the compounds described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824.

[0756] As a specific example of an onium salt compound (DD) that is a relatively weak acid relative to an acid generated from a photoacid generator, for example, the compound described in paragraphs

[0305] to

[0314] of International Publication No. 2020 / 158337 can be cited.

[0757] In addition to the above, for example, well-known compounds disclosed in paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458A1 may be used as acid diffusion control agents.

[0758] The molecular weight of the acid diffusion control agent is not particularly limited, but is preferably 100 to 3000, more preferably 150 to 2500, and even more preferably 200 to 2000.

[0759] The acid diffusion control agent is preferably a compound that produces an acid with a pKa of 0 or higher by irradiation with photochemical rays or radiation.

[0760] Acid diffusion control agents can be intramolecular salts.

[0761] The content of the acid diffusion control agent in the resist composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total solid content of the resist composition. Furthermore, the content of the acid diffusion control agent is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, and even more preferably 30.0% by mass or less, relative to the total solid content of the resist composition.

[0762] Acid diffusion control agents may be used in single or multiple forms. When using multiple forms, it is preferable that their total content is within the preferred content range described above.

[0763] When the resist composition contains a compound containing a sulfonium cation and an anion having an iodine atom as an acid diffusion control agent, the content of the compound containing the sulfonium cation and the anion having an iodine atom relative to the total amount of the acid diffusion control agent in the resist composition is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, and even more preferably 50 to 100% by mass.

[0764] When the resist composition contains a compound containing a sulfonium cation and an iodine atom as an acid diffusion control agent, only one compound containing a sulfonium cation and an iodine atom may be used, or two or more compounds may be used. When two or more compounds are used, it is preferable that their total content is within the preferred content range described above.

[0765] The photoacid generator and the acid diffusion control agent in the resist composition contain at least one sulfonium cation and an anion having an iodine atom.

[0766] The aforementioned sulfonium cation is preferably one containing a halogen atom.

[0767] The anion having the above-mentioned iodine atoms is preferably having two or more iodine atoms.

[0768] At least one of the photoacid generator and the acid diffusion control agent is preferably a sulfonium cation having halogen atoms and an anion having two or more iodine atoms.

[0769] [Hydrophobic resin]

[0770] The resist composition may further comprise a hydrophobic resin different from resin (A).

[0771] Hydrophobic resins are preferably designed to be present on the surface of the resist film, but unlike surfactants, they do not necessarily have hydrophilic groups in their molecules and may not contribute to the uniform mixing of polar and non-polar substances.

[0772] From the viewpoint of being predominantly present on the membrane surface, the hydrophobic resin is preferably composed of one or more of the following: fluorine atoms, silicon atoms, and a CH3 moiety included in the side chain portion of the resin; more preferably, it has two or more of these. The hydrophobic resin is preferably composed of hydrocarbon groups having five or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted in the side chain.

[0773] As a hydrophobic resin, the compounds described in paragraphs

[0275] to

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

[0774] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin relative to the total solid content of the resist composition is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 15.0% by mass.

[0775] One type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, it is preferable that their total content is within the preferred content range described above.

[0776] [surfactant]

[0777] The resist composition may contain a surfactant. When a surfactant is present, it can form a pattern with better adhesion and fewer development defects.

[0778] The surfactant is preferably a fluorinated and / or silicone surfactant.

[0779] As fluorinated and / or silicone surfactants, examples include the surfactants disclosed in paragraphs

[0218] and

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

[0780] When the resist composition contains a surfactant, the surfactant content is preferably 0.0001 to 2.0% by mass relative to the total solid content of the resist composition, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0781] One surfactant may be used, or two or more surfactants may be used. When two or more surfactants are used, it is preferable that their total content is within the preferred content range described above.

[0782] [solvent]

[0783] The resist composition contains a solvent.

[0784] The solvent is preferably composed of at least one of (M1) and (M2), wherein (M1) is a propylene glycol monoalkyl ether carboxylic acid ester, and (M2) is selected from at least one of the groups consisting of propylene glycol monoalkyl ethers, lactates, acetates, alkoxypropionates, chain ketones, cyclic ketones, lactones, and alkylene carbonates. Furthermore, the solvent may further contain components other than (M1) and (M2).

[0785] From the viewpoint of improving the coatability of the resist composition and reducing the number of development defects in the pattern, it is preferable to combine the aforementioned solvent and the aforementioned resin. Since the aforementioned resin has a good balance of solubility, boiling point and viscosity, the aforementioned solvent can suppress uneven film thickness of the resist film and the generation of precipitates during spin coating.

[0786] Details of ingredients (M1) and (M2) are set out in paragraphs

[0218] to

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

[0787] When the solvent further contains components other than components (M1) and (M2), the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of solvent.

[0788] The solvent content in the resist composition is preferably set such that the solid component concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass. This can further improve the coatability of the resist composition.

[0789] [Other Additives]

[0790] The resist composition may further comprise at least one selected from the group consisting of a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in the developer (e.g., a phenolic compound with a molecular weight of less than 1000, or an alicyclic or aliphatic compound containing a carboxyl group).

[0791] The aforementioned "dissolution-inhibiting compounds" refer to compounds with a molecular weight of less than 3000 that decompose through the action of acid, thereby reducing their solubility in organic developing solutions.

[0792] There are no particular restrictions on the content of other additives. Relative to the total solid content of the resist composition, it can be less than 20.0% by mass, less than 10.0% by mass, or less than 5.0% by mass.

[0793] Other additives may be used in single or multiple forms. When using multiple additives, it is preferable that their total content is within the aforementioned preferred content range.

[0794] In addition, the resist composition sometimes contains water as an impurity. When water is present as an impurity, the lower the water content, the better. It can be 1 to 30,000 ppm by mass relative to the total resist composition.

[0795] In addition, the resist composition sometimes contains residual monomers (e.g., monomers derived from the raw material monomers used in the synthesis of resin (A)) as impurities. When residual monomers are present as impurities, the content of residual monomers should be as low as possible, and may be 1 to 30,000 ppm by mass relative to the total solids content of the resist composition.

[0796] <Photosensitive or radiosensitive linear resin compositions>

[0797] The present invention also relates to a photosensitive radioactive or radiosensitive linear resin composition (also referred to as "the composition of the present invention"), comprising a resin (A) whose polarity is increased by the action of an acid, a photoacid generator, an acid diffusion control agent, and a solvent, wherein at least one of the photoacid generator and the acid diffusion control agent comprises a sulfonium cation and an anion having an iodine atom, wherein...

[0798] The photosensitive radioactive or radiosensitive linear resin composition is used to form patterns by developing with an organic processing solution containing butyl acetate and hydrocarbons having 9 or more but less than 12 carbon atoms.

[0799] The composition of the present invention is the same as the photosensitive radioactive or radiosensitive linear resin composition used in step (1) of the pattern forming method of the present invention described above. Furthermore, the organic processing liquid containing butyl acetate and hydrocarbons having 9 or more and 12 or fewer carbon atoms is also the same as the organic processing liquid used in step (3) of the pattern forming method of the present invention described above.

[0800] <Methods for Manufacturing Electronic Devices>

[0801] This specification also relates to a method for manufacturing an electronic device including the above-described pattern forming method, and an electronic device manufactured by the method.

[0802] As a preferred embodiment of the electronic device described in this specification, it may be mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[0803] [Example]

[0804] The present invention will now be described in more detail based on embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0805] The following shows the various components used in the resist compositions of the examples and comparative examples.

[0806] <Resin (A)>

[0807] As resin (A), Pol-01 to Pol-22 were used.

[0808] Pol-01 to Pol-22 contain the repeating units shown in Table 1 below in the amounts shown in Table 1 below. Table 1 also lists the weight-average molecular weight (Mw) and dispersity (Mw / Mn) of each resin. The content of each repeating unit is the molar ratio of each repeating unit contained in each resin relative to all repeating units.

[0809] The weight-average molecular weight (Mw) and dispersibility (Mw / Mn) of the resin were determined by GPC (carrier: tetrahydrofuran (THF)) (converted to polystyrene). Additionally, the following were determined by... 13 The content of repeating units was determined by C-NMR (nuclear magnetic resonance).

[0810] [Table 1]

[0811]

[0812] The following shows the structural formula of the repeating unit.

[0813] [Chemical Formula 35]

[0814]

[0815] [Chemical Formula 36]

[0816]

[0817] [Chemical Formula 37]

[0818]

[0819] U-01 to U-18, U-40, U-42, U-43 and U-44 are repeating units with acid-decomposing groups.

[0820] U-38 and U-41 are repeating units having groups that generate acid upon irradiation by photochemical rays or radiation. Pol-14 and Pol-15, which contain either U-38 or U-41, are also photoacid generators. That is, Pol-14 and Pol-15 serve as both resin (A) and photoacid generator. For convenience, in Table 4 below, Pol-14 and Pol-15 are listed only in the "Resin (A)" column and not in the "Photoacid Generator" column.

[0821] <Photoacid generator>

[0822] PAG-1 to PAG-49 were used as photoacid generators. Me indicates methyl.

[0823] [Chemical Formula 38]

[0824]

[0825] [Chemical Formula 39]

[0826]

[0827] [Chemical Formula 40]

[0828]

[0829] [Chemical Formula 41]

[0830]

[0831] [Chemical Formula 42]

[0832]

[0833] [Chemical Formula 43]

[0834]

[0835] [Chemical Formula 44]

[0836]

[0837] [Chemical Formula 45]

[0838]

[0839] <Acid Diffusion Control Agent>

[0840] Q-1 to Q-35 were used as acid diffusion control agents.

[0841] [Chemical Formula 46]

[0842]

[0843] [Chemical Formula 47]

[0844]

[0845] [Chemical Formula 48]

[0846]

[0847] [Chemical Formula 49]

[0848]

[0849] [Chemical Formula 50]

[0850]

[0851] <Solvent>

[0852] The solvents used are shown below.

[0853] F-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0854] F-2: Propylene glycol monomethyl ether (PGME)

[0855] F-3: Propylene glycol monoethyl ether (PGEE)

[0856] F-4: Cyclohexanone

[0857] F-5: Cyclopentanone

[0858] F-6: 2-Heptanone

[0859] F-7: Ethyl lactate

[0860] F-8: γ-Butyrolactone

[0861] F-9: Propylene carbonate

[0862] <Organic Treatment Liquid>

[0863] The organic treatment solutions used are shown in Table 2 below. The contents of the first and second solvents in Table 2 are the mass ratios of each solvent relative to the total organic treatment solution.

[0864] [Table 2]

[0865]

[0866] <Preparation of the resist composition>

[0867] The components shown in Tables 3 and 4 below were dissolved in the solvents shown in the tables to prepare a solution, and the solution was filtered through a polyethylene filter with a pore size of 0.02 μm to prepare the resist composition (RE-1 to RE-58).

[0868] In the table, the "Content (mass%)" column shows the content (mass%) of each component relative to the total solids content in the resist composition. Solids content refers to components other than the solvent.

[0869] In the table, when more than one ingredient is used, the type and amount of each ingredient are separated by " / ". The order in which the types and amounts separated by " / " are recorded corresponds to the order in which they are listed.

[0870] [Table 3]

[0871]

[0872] [Table 4]

[0873]

[0874] [Examples 01 to 60, Comparative Examples 1 to 5]

[0875] <Pattern Formation Method (1): EUV Exposure, Organic Solvent Development (Negative Type)>

[0876] Organic film AL412 (manufactured by Brewer Science) was coated onto a silicon wafer and baked at 205°C for 60 seconds to form a film with a thickness of 5 nm. The various photoresist compositions shown in Tables 5 and 6 were then coated onto the wafer and baked at the temperatures shown in Tables 5 and 6 for 60 seconds (PB) to form a photoresist film with a thickness of 45 nm.

[0877] Using an EUV exposure apparatus (Exitech Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) as the exposure source, and an exposure mask (line / space = 1 / 1), the entire surface of the wafer with the resist film formed above was patterned with the same and uniform exposure. After exposure, it was baked (PEB) for 60 seconds on a hot plate at the temperatures described in Tables 5 and 6. Then, it was developed for 30 seconds using the organic developer shown in Tables 5 and 6, and then rotated to dry, obtaining a negative pattern.

[0878] The LWR performance of the pattern obtained by the above patterning method is evaluated using the following method. Furthermore, the etch resistance is evaluated using the exposure source described in the above patterning method using the following method.

[0879] [evaluate]

[0880] The obtained line and spatial patterns were observed using a length-measuring scanning electron microscope (SEM, Hitachi S-9380II). The exposure amount at which the 1:1 line and spatial pattern with a linewidth of 20 nm was resolved was set as the sensitivity (Eop).

[0881] [LWR Performance]

[0882] For a 1:1 line and spatial pattern with a linewidth of 20 nm resolved using the exposure amount representing the aforementioned sensitivity (Eop), calculate 3 times the standard deviation (σ) of the measured linewidth, i.e., 3σ (nm), and set this as the index of LWR. Specifically, an exposure area (Shot) of 3.5 mm in the longitudinal (y-axis direction) and 6.5 mm in the transverse (x-axis direction) is defined as a single exposure area. Exposure is performed on 232 exposure areas on the wafer, consisting of 8 columns in the x-axis and 29 rows in the y-axis direction. Ten length measurement images (five lines per image) are taken from each exposure area, and the average of the ten length measurement values ​​is taken as the length measurement value for that exposure area. The standard deviation of the length measurement values ​​of the 232 exposure areas is multiplied by 3, which is set as 3σ. Based on the obtained 3σ value, LWR is evaluated according to the following evaluation criteria.

[0883] The LWR is evaluated based on the following ten-level criteria. Furthermore, a LWR of 6 or below is considered good, preferably 3 or below, and more preferably 1.

[0884] (Evaluation Criteria)

[0885] 1: Deviation 3σ is less than 2.4nm.

[0886] 2: Deviation 3σ is greater than 2.4nm and less than 2.6nm.

[0887] 3: Deviation 3σ is greater than 2.6nm and less than 2.8nm.

[0888] 4: Deviation 3σ is greater than 2.8nm and less than 3.0nm.

[0889] 5: Deviation 3σ is greater than 3.0nm and less than 3.2nm.

[0890] 6: Deviation 3σ is greater than 3.2nm and less than 3.4nm.

[0891] 7: Deviation 3σ is greater than 3.4nm and less than 3.6nm.

[0892] 8: Deviation 3σ is greater than 3.6nm and less than 3.8nm.

[0893] 9: Deviation 3σ is greater than 3.8nm and less than 4.0nm.

[0894] 10: Deviation 3σ is greater than 4.0 nm.

[0895] Exposure tolerance (EL)

[0896] Using the sensitivity (Eop) mentioned above as a benchmark, the exposure is calculated when the linewidth is ±10% of the target value of 20nm (i.e., 22nm and 18nm). Then, the exposure latitude (EL, unit: %) is calculated as defined by the following formula. The larger the EL value, the smaller the performance change caused by the change in exposure, and the better.

[0897] EL (%) = [[(exposure when the line width is 22nm) - (exposure when the line width is 18nm)] / Eop] × 100

[0898] EL is evaluated according to the following evaluation criteria.

[0899] The EL performance is evaluated according to the criteria A to D below. Furthermore, B or above is considered good EL performance, and A is more preferred.

[0900] (Evaluation Criteria)

[0901] A: EL is greater than 25%.

[0902] B: EL is greater than 20% and less than 25%.

[0903] C: EL is greater than 15% and less than 20%.

[0904] D:EL is below 15%.

[0905] The results are shown in Tables 5 and 6 below.

[0906] [Table 5]

[0907]

[0908] [Table 6]

[0909]

[0910] The results above show that the resist composition used in the examples and the pattern forming method of the examples have excellent exposure tolerance and LWR performance.

[0911] [Industry availability]

[0912] According to the present invention, a pattern forming method with excellent exposure latitude and LWR performance, as well as a photosensitive radioactive or radiosensitive linear resin composition, can be provided. Furthermore, according to the present invention, a method for manufacturing an electronic device including the above-described pattern forming method can be provided.

[0913] Although the invention has been described in detail 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.

[0914] This application is based on Japanese Patent Application No. 2024-055669, filed on March 29, 2024, the contents of which are incorporated herein by reference.

Claims

1. A method for forming a pattern, comprising: (1) A step of forming a film using a photosensitive radioactive or radioactive linear resin composition, wherein the photosensitive radioactive or radioactive linear resin composition contains a resin (A) whose polarity is increased by the action of an acid, a photoacid generator, an acid diffusion control agent, and a solvent, and at least one of the photoacid generator and the acid diffusion control agent contains a sulfonium cation and an anion having an iodine atom. (2) The process of exposing the film; as well as (3) A process of developing the exposed film using an organic processing solution containing butyl acetate and hydrocarbons with 9 or more but less than 12 carbon atoms.

2. The pattern forming method according to claim 1, wherein, The photoacid generator and the acid diffusion control agent comprise sulfonium cations and monovalent anions having only one anionic site.

3. The pattern forming method according to claim 1, wherein, The photoacid generator comprises at least one selected from the group consisting of -O-CO-, -O-CO-O-, and -O-.

4. The pattern forming method according to claim 1, wherein, The acid diffusion control agent comprises a carboxylate.

5. The pattern forming method according to claim 1, wherein, The sulfonium cation has halogen atoms.

6. The pattern forming method according to claim 1, wherein, The anion containing iodine atoms has two or more iodine atoms.

7. The pattern forming method according to claim 1, wherein, The resin (A) contains repeating units having iodine atoms.

8. The pattern forming method according to claim 6, wherein, At least one of the photoacid generator and the acid diffusion control agent comprises a sulfonium cation having a halogen atom and an anion having two or more iodine atoms.

9. A photosensitive or radiosensitive linear resin composition comprising a resin (A) whose polarity increases through the action of an acid, a photoacid generator, an acid diffusion control agent, and a solvent, wherein at least one of the photoacid generator and the acid diffusion control agent comprises a sulfonium cation and an anion having an iodine atom. The photosensitive radioactive or radiosensitive linear resin composition is used to form patterns by developing with an organic processing solution containing butyl acetate and hydrocarbons having 9 or more but less than 12 carbon atoms.

10. The photosensitive radioactive or radiosensitive linear resin composition according to claim 9, wherein, The photoacid generator and the acid diffusion control agent comprise sulfonium cations and monovalent anions having only one anionic site.

11. The photosensitive radioactive or radiosensitive linear resin composition according to claim 9, wherein, The photoacid generator comprises at least one selected from the group consisting of -O-CO-, -O-CO-O-, and -O-.

12. The photosensitive radioactive or radiosensitive linear resin composition according to claim 9, wherein, The acid diffusion control agent comprises a carboxylate.

13. The photosensitive radioactive or radiosensitive linear resin composition according to claim 9, wherein, The sulfonium cation has halogen atoms.

14. The photosensitive radioactive or radiosensitive linear resin composition according to claim 9, wherein, The anion containing iodine atoms has two or more iodine atoms.

15. The photosensitive radioactive or radiosensitive linear resin composition according to claim 9, wherein, The resin (A) contains repeating units having iodine atoms.

16. A method for manufacturing an electronic device, comprising the pattern forming method according to any one of claims 1 to 8.

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