Method for producing actinic ray-sensitive or radiation-sensitive resin composition, pattern formation method, and method for producing electronic device

Abstract

Provided are: a method for producing an actinic ray-sensitive or radiation-sensitive resin composition, said method including a step (X) for filtering an actinic ray-sensitive or radiation-sensitive resin composition containing a solvent and a resin (A) of which the main chain is decomposed by being irradiated with actinic rays or radiation, and performing the filtering by passing said composition through two or more types of filters; a pattern formation method that uses the method for producing an actinic ray-sensitive or radiation-sensitive resin composition; and a method for producing an electronic device.

Description

Method for producing actinic ray-sensitive or radiation-sensitive resin composition, method for forming pattern, and method for producing electronic device

[0001] The present invention relates to a method for producing an actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for producing an electronic device.

[0002] Since the development of resists for KrF excimer lasers (248 nm), pattern formation methods utilizing chemical amplification have been used to compensate for the loss of sensitivity due to light absorption. For example, in positive-tone chemical amplification methods, a photoacid generator contained in the exposed area decomposes upon light irradiation to generate acid. Then, during a post-exposure bake (PEB) process, the catalytic action of the generated acid changes the alkali-insoluble groups of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition to alkali-soluble groups, thereby changing the solubility in the developer. Development is then performed, for example, using a basic aqueous solution. This removes the exposed areas to obtain the desired pattern. To achieve miniaturization of semiconductor elements, the wavelength of exposure light sources has become shorter and the numerical aperture (NA) of projection lenses has become higher. Currently, exposure machines using an ArF excimer laser with a wavelength of 193 nm as a light source have been developed. Recently, pattern formation methods using extreme ultraviolet (EUV) and electron beam (EB) as light sources have also been studied. Under these circumstances, various configurations have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.

[0003] Also known is a pattern formation method using a resin whose main chain is cleaved by irradiation with actinic rays or radiation (main chain decomposition type resin).

[0004] Patent Document 1 describes a method for producing a positive resist composition, which includes a step of filtering a solution containing a copolymer containing monomer units having a specific structure and a solvent through a filter with a particle size exclusion diameter of 20 nm or less, thereby reducing the amount of foreign matter such as metals. Patent Document 2 describes a method for producing a resin-containing composition containing a resin having an acid labile group and a solvent, which includes a step of circulating and filtering the composition containing the resin having an acid labile group and the solvent through a filter equipped with a membrane of a specific pore size and material.

[0005] Japanese Patent Publication No. 2022-100128 Japanese Patent Publication No. 2022-167867

[0006] Recently, due to the trend toward finer patterns, the performance required of resist compositions has become increasingly higher. In particular, further improvement in line width roughness (LWR) performance is required. LWR performance refers to the ability to reduce the LWR of a pattern.

[0007] An object of the present invention is to provide a method for producing an actinic ray-sensitive or radiation-sensitive resin composition having excellent LWR performance. Another object of the present invention is to provide a pattern formation method and a method for producing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

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

[0009] [1] A method for producing an actinic ray-sensitive or radiation-sensitive resin composition, comprising: a step (X) of filtering an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) whose main chain is decomposed by irradiation with actinic rays or radiation and a solvent through two or more types of filters. [2] A method for producing the actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the resin (A) contains at least one of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2):

[0010]

[0011] In formula (1), R １ represents a halogen atom, a cyano group, an alkylsulfonyl group, an alkoxy group, a nitro group, an acyl group, an alkyl ester group, a halogenated alkyl group, or a halogenated cycloalkyl group. ２ and R ３ R each independently represents a hydrogen atom or a substituent. ４ represents a substituent. ２ or R ３ and R ４ may be bonded to form a ring.

[0012]

[0013] In formula (2), R ５ represents a hydrogen atom, a halogen atom or an organic group. ６ and R ７ Each independently represents a hydrogen atom or an organic group. １ represents a benzene ring group or a naphthalene ring group. ８ represents a substituent. k represents an integer of 0 to 7. R ８ If there are multiple R ８ may be the same or different, and R ８ and (2-m) represents a repeating unit represented by the formula (1-m) below, and a compound represented by the formula (2-m) below, and the total content of the compound represented by the formula (1-m) below and the compound represented by the formula (2-m) below in the actinic ray-sensitive or radiation-sensitive resin composition before filtering in the step (X) is 1 to 30,000 ppm by mass, relative to the total mass of the composition.

[0014]

[0015] In formula (1-m), R １represents a halogen atom, a cyano group, an alkylsulfonyl group, an alkoxy group, a nitro group, an acyl group, an alkyl ester group, a halogenated alkyl group, or a halogenated cycloalkyl group. ２ and R ３ R each independently represents a hydrogen atom or a substituent. ４ represents a substituent. ２ or R ３ and R ４ may be bonded to form a ring.

[0016]

[0017] In formula (2-m), R ５ represents a hydrogen atom, a halogen atom or an organic group. ６ and R ７ Each independently represents a hydrogen atom or an organic group. １ represents a benzene ring group or a naphthalene ring group. ８ represents a substituent. k represents an integer of 0 to 7. R ８ If there are multiple R ８ may be the same or different, and R ８They may be bonded to each other to form a ring. [5] The method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the weight-average molecular weight of the resin (A) in the actinic ray-sensitive or radiation-sensitive resin composition before filtering in step (X) is 20,000 or more. [6] The method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein at least two of the filters have different pore sizes, with a filter having a relatively large pore size and a filter having a relatively small pore size being arranged in this order on the filtration flow path. [7] The method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the first of the filters arranged on the filtration flow path has a pore size of 20 nm or less. [8] The method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the first of the filters arranged on the filtration flow path has a pore size of 5 nm or more. [9] A method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the pore size of the second or subsequent filter in the filtration flow path is 5 nm or less.

[10] A method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein step (X) comprises a step of circulating the actinic ray-sensitive or radiation-sensitive resin composition that has passed through the filter and passing it through the same filter again.

[11] A pattern formation method comprising the steps of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition produced by the production method according to any one of [1] to

[10] , exposing the resist film to light, and developing the exposed resist film with a developer.

[12] A method for producing an electronic device, comprising the pattern formation method according to

[11] .

[0018] According to the present invention, there is provided a method for producing an actinic ray-sensitive or radiation-sensitive resin composition having excellent LWR performance. Furthermore, according to the present invention, there is provided a pattern formation method and a method for producing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

[0019] FIG. 1 is a schematic diagram of an example of a purification apparatus capable of carrying out the production method of the present invention.

[0020] The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, when a group (atomic group) is referred to without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" encompasses 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. Unless otherwise specified, the substituent is preferably a monovalent substituent. Examples of the substituent include monovalent nonmetallic atomic groups excluding hydrogen atoms, which can be selected, for example, from the following substituents T:

[0021] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, an acryloyloxy ... Examples of the substituent T include acyl groups such as an alkyl group, a methacryloyl group, and a methoxalyl group; a sulfanyl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; an aromatic heterocyclic group (heteroaryl group); a hydroxy group; a carboxyl group; a formyl group; a sulfo group; a cyano group; an alkylaminocarbonyl group; an arylaminocarbonyl group; a sulfonamide group; a silyl group; an amino group; a carbamoyl group; and the like. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (for example, a monoalkylamino group, a dialkylamino group, an arylamino group, a trifluoromethyl group, etc.).

[0022] As used herein, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beams). As used herein, "light" refers to actinic rays or radiation. Unless otherwise specified, "exposure" as used herein includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams. As used herein, the term "to" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits. The bonding direction of divalent groups described herein is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be either -CO-O- or -O-CO-. In addition, the compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0023] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) using a GPC apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0024] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​determined by calculation using this software package.

[0025] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0026] On the other hand, pKa can also be determined by molecular orbital calculation. A specific method for this is to calculate the pKa of H in an aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate the dissociation free energy. ＋ The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, and Gaussian 16 is an example.

[0027] As described above, the pKa in this specification refers to a value calculated using software package 1 based on a database of Hammett's substituent constants and publicly known literature values, but if the pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be used. Furthermore, as described above, the pKa in this specification refers to "pKa in aqueous solution," but if the pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be used.

[0028] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0029] In this specification, the term "solid content" refers to components that form a resist film and does not include solvents. Furthermore, any component that forms a resist film is considered to be a solid content even if it is in a liquid state.

[0030] [Method for Producing Actinic Ray- or Radiation-Sensitive Resin Composition] The method for producing an actinic ray- or radiation-sensitive resin composition of the present invention (also referred to as the "production method of the present invention") is a method for producing an actinic ray- or radiation-sensitive resin composition, comprising step (X) of filtering an actinic ray- or radiation-sensitive resin composition containing a resin (A) whose main chain decomposes upon irradiation with actinic rays or radiation and a solvent through two or more filters. The actinic ray- or radiation-sensitive resin composition is typically a resist composition. The actinic ray- or radiation-sensitive resin composition is also referred to as a "resist composition." The actinic ray- or radiation-sensitive resin composition (resist composition) before performing step (X) is also referred to as a "composition (S1)." The actinic ray- or radiation-sensitive resin composition (resist composition) after performing step (X) is also referred to as a "composition (S2)."

[0031] The reason why the composition (S2) produced by the production method of the present invention has excellent LWR performance is not fully understood, but the inventors speculate as follows. However, the present invention is not limited by the following speculated mechanism. Alternating copolymers commonly used as main-chain decomposition resins tend to contain residual monomer components during synthesis or purification. If residual monomer components remain in the resist composition, they may act as nuclei for material aggregation during application to a substrate, resulting in in-plane variations in the material, or as penetration sites for the developer, causing non-uniform development and resulting in worsened roughness. In the process of filtering a resist composition containing a main-chain decomposition resin through a filter, gelling a portion of the polymer components on the filter is believed to allow monomer components with different polarities (philicity / phobicity) relative to the polymer to be incorporated into the gel, thereby enabling efficient removal. However, excessive gel components can clog the filter, preventing efficient removal of the monomer components. Pattern formation using a main-chain decomposition resin utilizes the difference in molecular weight before and after decomposition of the polymer main chain. Therefore, the main-chain decomposition resin generally has a higher weight-average molecular weight than the acid-decomposable resin used in pattern formation methods that utilize the polarity conversion of the resin due to the action of acid. Therefore, the main-chain decomposition resin contains a higher amount of ultra-high molecular weight components (gelling components) than other resins. In the present invention, it is believed that the use of two or more types of filters can remove both the gelling components and the monomer components, thereby improving LWR performance.

[0032] [Step (X)] Step (X) is a step of filtering an actinic ray- or radiation-sensitive resin composition (composition (S1)) containing resin (A) and a solvent by passing it through two or more types of filters. Two or more types of filters are used in step (X). That is, at least two different types of filters are used in step (X). With regard to filters, "different types" means that at least one of the pore size and material (material constituting the filter) of the filter is different. Therefore, at least two filters are used in step (X), and the at least two filters differ in at least one of the pore size and material.

[0033] In the manufacturing method of the present invention, it is preferable that at least two of the two or more filters have different pore sizes, and that a filter with a relatively large pore size and a filter with a relatively small pore size are arranged in this order on the filtration flow path. The filtration flow path is a flow path through which the resist composition passes in step (X).

[0034] (Pore diameter of filter) In the manufacturing method of the present invention, the pore diameter of the first filter arranged in the filtration flow path among two or more types of filters ("F Ｐ１ " is also referred to as ". The pore size of the first filter disposed on the filtration flow path is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or less. The pore size of the first filter disposed on the filtration flow path is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more.

[0035] In the manufacturing method of the present invention, among two or more types of filters, the pore size of the second or subsequent filter arranged on the filtration flow path ("F Ｐ２ " is also referred to as ". The pore size of the second or subsequent filter disposed on the filtration flow path may be 1 nm or more.

[0036] In the manufacturing method of the present invention, F Ｐ１is 5 nm or more and 20 nm or less, and F Ｐ２ is 5 nm or less, and F Ｐ１ is F Ｐ２ (i.e., F Ｐ２ is F Ｐ１ It is preferable that the F Ｐ１ It is considered that when the particle size is 5 nm or more and 20 nm or less, the gelling components in the composition (S1) can be removed to some extent, and clogging of the filter can be suppressed. Ｐ２ is F Ｐ１ and F Ｐ２ It is believed that by keeping the thickness of the film at 5 nm or less, the monomer component can be efficiently removed, thereby improving the LWR performance. Ｐ１ and F Ｐ２ F Ｐ２ / F Ｐ１ is preferably 0.5 or less, and more preferably 0.2 or less. For commercially available products, the manufacturer's nominal value is used for the pore size of the filter. For non-commercial products or when the manufacturer's nominal value cannot be confirmed, isopropanol (IPA) or HFE-7200 ("Novec 7200", manufactured by 3M, hydrofluoroether, C ４ F ９ O.C. ２ H ５ ) means the pore size determined by the bubble point of the

[0037] (Filter material) The filter material is not particularly limited, but when it is a polymer, it preferably contains 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); polyamideimide; polyesters such as polyethylene terephthalate; polyethersulfone; cellulose; polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane and other polyfluorocarbons; derivatives of the above polymers; etc., and more preferably comprises at least one selected from the group consisting of polyolefins, polyamides, polyimides, polyamideimides, polyesters, polysulfones, cellulose, polyfluorocarbons and their derivatives. In addition to resins, it may also be diatomaceous earth, glass, etc.

[0038] The filter material may be a polymer derivative. Typical examples of derivatives include those obtained by introducing ion exchange groups into the above polymers through chemical modification treatment. The ion exchange groups may be cation exchange groups or anion exchange groups. Examples of cation exchange groups include sulfonic acid groups, carboxyl groups, and phosphate groups, and examples of anion exchange groups include secondary, tertiary, and quaternary ammonium groups. The method for introducing ion exchange groups into a polymer is not particularly limited, but includes a method in which a compound having an ion exchange group and a polymerizable group is reacted with the polymer to typically perform grafting.

[0039] The filter may also be surface-treated other than chemically modified. The surface treatment method is not particularly limited and known methods can be used. Examples of surface treatment methods include plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

[0040] The materials of the two or more filters may be the same or different, but it is a preferred embodiment that the materials of at least two of the two or more filters are different. For example, the materials of the first filter arranged in the filtration flow path and the second filter arranged in the filtration flow path may be different. More specifically, for example, the material of the first filter arranged in the filtration flow path may be polyamide, and the material of the second filter arranged in the filtration flow path may be polyethylene.

[0041] The pore structure of the filter is not particularly limited, and refers to the pore size distribution, the positional distribution of the pores in the filter, the shape of the pores, and the like.

[0042] The shape of the filter is not particularly limited, and may be, for example, a disk shape, a pleated shape, etc. The number of layers of the filter is not particularly limited, and may be a single-layer film or a laminated film.

[0043] The temperature at which the resist composition is passed through the filter is not particularly limited, and may be, for example, room temperature (25° C.) or lower.

[0044] The filtration rate is not particularly limited, but may be, for example, 1.0 L / min / m ２ More than 0.75 L / min / m ２ More preferably, 0.6 L / min / m ２ The above is more preferable. The filter may have a pressure tolerance setting that ensures the filter performance (the filter will not break), and if this value is large, the filtration speed can be increased by increasing the filtration pressure. In other words, the upper limit of the filtration speed usually depends on the pressure tolerance of the filter, but is preferably, for example, 10.0 L / min / m ２ It may be the following:

[0045] Step (X) preferably includes a step of circulating the resist composition that has passed through two or more types of filters, and passing it again through at least one of the same two or more types of filters (that is, step (X) is preferably a step of performing circulating filtration. The circulating filtration will be described later).

[0046] (Purification Apparatus) Figure 1 is a schematic diagram of an example of a purification apparatus capable of carrying out the production method of the present invention. Purification apparatus 10 has a tank 11, a filtration apparatus 16, and a filling apparatus 13, and the above-mentioned units are connected by a pipeline 14. Filtration apparatus 16 has filter units 12(a) and 12(b) connected by a pipeline 14. A control valve 15(a) is arranged in the pipeline between the above-mentioned filter units 12(a) and 12(b).

[0047] 1, the resist composition (composition (S1)) to be purified is stored in a tank 11. Next, a pump (not shown) disposed in a pipeline 14 is operated, and the product to be purified is sent from the tank 11 through the pipeline 14 to a filtering device 16. The direction of transfer of the product to be purified in the purification device 10 is indicated by F in FIG. １ As shown.

[0048] The filtration device 16 comprises filter units 12(a) and 12(b) connected by a pipe 14, each of which houses a filter cartridge having a filter.

[0049] In the filtration device 16, an adjustment valve 15(a) is disposed on the upstream side (forward in the filtration flow path) of the filter unit 12(b), but the purification device capable of carrying out the production method of the present invention is not limited to this configuration and may also be configured such that an adjustment valve is disposed on the upstream side of the filter unit 12(a). Furthermore, any device capable of adjusting the supply pressure of the product to be purified other than an adjustment valve may be used. Examples of such components include a damper. Furthermore, the purification device capable of carrying out the production method of the present invention does not necessarily have to have an adjustment valve 15(a).

[0050] In the purification device 10, the supply pressure is adjusted by the adjusting valve 15(a), but this is not limited to the above. The supply pressure may be adjusted by at least one of the shape and filtration area of ​​the filter without using an adjusting valve. Specifically, one example is a method of configuring the filter to have a larger filtration area, for example, by pleating the filter.

[0051] In the filtration device 16, each filter forms a filter cartridge, but the filters that can be used in the production method of the present invention are not limited to the above-mentioned form. For example, the product to be purified may be passed through a filter formed in a flat plate shape.

[0052] The resist composition (composition (S2)) that has passed through the filtering device 16 is transferred to the filling device 13 and placed in a container.

[0053] A filtration method in which two or more types of filters are arranged in one filtration flow path, such as the purification apparatus 10 in FIG. 1, is also called "multistage filtration."

[0054] The purification apparatus for carrying out the production method of the present invention is not limited to the above, and may be configured, for example, so that the purified product filtered through filter unit 12(b) is returned to tank 11 and then passed through filter units 12(a) and 12(b) again. A filtration method in which the purified product is passed through a filtration flow path in which two or more types of filters are arranged, and then the filtration flow path is connected to the primary side of an arbitrary filter (which may be the first filter arranged in the filtration flow path, or a second or subsequent filter), thereby passing the purified product through the same filter again, is also called "circulating filtration." In purifying a purified product by circulating filtration, at least one of the two or more types of filters is used more than once.

[0055] Furthermore, a purification apparatus for carrying out the production method of the present invention may be one in which the product to be purified is passed through a filtration flow path provided with at least one filter of at least one type, filtered, and then the product to be purified is removed and filtered by passing the removed product through a filtration flow path provided with at least one filter of at least one type different from the filter described above (such a filtration method is also referred to as "multiple-pass filtration"). Due to the adjustment of the filtration pressure, multiple-pass filtration may be able to filter more efficiently than other filtration methods.

[0056] Next, various components contained in the actinic ray-sensitive or radiation-sensitive resin composition (resist composition) will be described.

[0057] [Composition (S1)] The composition (S1), which is an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) to be subjected to step (X) in the production method of the present invention, will now be described.

[0058] (Resin (A)) The composition (S1) contains a resin (A) whose main chain decomposes when irradiated with actinic rays or radiation. The resin (A) is preferably a resin whose main chain decomposes when irradiated with X-rays, electron beams, or extreme ultraviolet rays. The resin (A) preferably contains at least one of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and more preferably contains a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

[0059]

[0060] In formula (1), R １ represents a halogen atom, a cyano group, an alkylsulfonyl group, an alkoxy group, a nitro group, an acyl group, an alkyl ester group, a halogenated alkyl group, or a halogenated cycloalkyl group. ２ and R ３ R each independently represents a hydrogen atom or a substituent. ４ represents a substituent. ２ or R ３ and R ４ may be bonded to form a ring.

[0061]

[0062] In formula (2), R ５ represents a hydrogen atom, a halogen atom or an organic group. ６ and R ７ Each independently represents a hydrogen atom or an organic group. １ represents a benzene ring group or a naphthalene ring group. ８ represents a substituent. k represents an integer of 0 to 7. R ８ If there are multiple R ８ may be the same or different, and R ８ They may be bonded to each other to form a ring.

[0063] In formula (1), R １represents a halogen atom, a cyano group, an alkylsulfonyl group, an alkoxy group, a nitro group, an acyl group, an alkyl ester group, a halogenated alkyl group, or a halogenated cycloalkyl group, and preferably represents a halogen atom, a fluorinated alkyl group, or a fluorinated cycloalkyl group. １ The halogen atom represented by R is preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a chlorine atom. １ The alkyl group in the fluorinated alkyl group represented by the formula (I) may be either linear or branched. The alkyl group may have one or more fluorine atoms substituted thereon, but is preferably a perfluoroalkyl group. １ The number of carbon atoms in the fluorinated alkyl group represented by R is not particularly limited, but is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. １ The cycloalkyl group in the fluorinated cycloalkyl group represented by the formula (I) may be either a monocyclic or polycyclic group. The cycloalkyl group may have one or more fluorine atoms substituted thereon, but may also be a perfluorocycloalkyl group. １ The number of carbon atoms in the fluorinated cycloalkyl group represented by the formula (I) is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. １ preferably represents a halogen atom, more preferably a fluorine atom, a chlorine atom or a bromine atom, and even more preferably a chlorine atom.

[0064] R in formula (1) ２ and R ３ R each independently represents a hydrogen atom or a substituent. ２ and R ３The substituent represented by is not particularly limited, but is preferably an organic group, and more preferably an alkyl group or a cycloalkyl group. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is, for example, preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is, for example, preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. The alkyl group and the cycloalkyl group may have a substituent. The substituent is not particularly limited, but examples include a halogen atom (preferably a fluorine atom or an iodine atom), a hydroxy group, a carboxyl group, an amino group, an amide group, an imide group, a thiol group, an acetyl group, a sulfonic acid group, a sulfonamide group, and an acetoxy group. R ２ and R ３ is preferably a hydrogen atom.

[0065] R in formula (1) ４ represents a substituent. ４ The substituent represented by the formula (1-1) is not particularly limited, and examples thereof include a group represented by the formula (1-1) below, a hydroxy group, -NH ２ etc.

[0066] Formula (1-1): *-L １Ａ -R １Ａ

[0067] In formula (1-1), * represents a bonding position. １Ａ is a single bond, —O— or —N(R ｘ )-. ｘ represents a hydrogen atom or an organic group. ｘThe organic group represented by the formula (I) is not particularly limited, but is preferably, for example, an alkyl group or a cycloalkyl group. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is, for example, preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is, for example, preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. The alkyl group and the cycloalkyl group may have a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom), a hydroxy group, a carboxyl group, an amino group, an amide group, an imide group, a thiol group, an acetyl group, a sulfonic acid group, a sulfonamide group, and an acetoxy group. R ｘ is preferably a hydrogen atom.

[0068] In formula (1-1), R １Ａ represents a hydrogen atom or an organic group. １ＡThe organic group represented by the formula (I) is not particularly limited, but examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a group containing an onium salt structure, as described below. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably, for example, 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is, for example, preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The alkyl group and the cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom), a hydroxy group, a carboxyl group, an amino group, an amide group, an imide group, a thiol group, an acetyl group, a sulfonic acid group, a sulfonamide group, and an acetoxy group.

[0069] In addition, one embodiment of the alkyl group is —C(R Ｘ１ ) (R Ｘ２ ) (R Ｘ３ ) groups represented by R Ｘ１ ~R Ｘ３ R each independently represents an alkyl group or a cycloalkyl group. Ｘ１ ~R Ｘ３ The alkyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, and is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Ｘ１ ~R Ｘ３The cycloalkyl group represented by the formula (I) may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 5 to 15, and more preferably 5 to 10. The cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. R Ｘ１ ~R Ｘ３ each independently represents a linear or branched alkyl group (preferably a linear alkyl group), or R Ｘ１ ~R Ｘ３ Preferably, two of the R Ｘ１ ~R Ｘ３ The alkyl group or cycloalkyl group represented by the formula (I) may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom), a hydroxyl group, a carboxyl group, an amino group, an amide group, an imide group, a thiol group, an acetyl group, a sulfonic acid group, a sulfonamide group, and an acetoxy group. Ｘ１ ) (R Ｘ２ ) (R Ｘ３ ) represents a group represented by the above L １Ａ As the group, —O— or —N(R Ｘ )-, and more preferably -O-.

[0070] The aryl group may be either monocyclic or polycyclic, and is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. Of these, the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may also have a substituent. The substituent is not particularly limited, and examples include a halogen atom (preferably a fluorine atom or an iodine atom), a hydroxy group, a carboxyl group, an amino group, an amide group, an imide group, a thiol group, an acetyl group, a sulfonic acid group, a sulfonamide group, and an acetoxy group. Of these, a fluorine atom, an iodine atom, or a hydroxy group is preferred.

[0071] The aralkyl group preferably has a structure in which one of the hydrogen atoms in the alkyl group is substituted with the aryl group, and the number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 15.

[0072] In formula (1), R ２ or R ３ and R ４ may be bonded to form a ring. ２ or R ３ and R ４ and are bonded to each other to form a ring containing at least two carbon atoms and one carbonyl (>C=O) carbon atom as specified in formula (1), and is preferably a 5- to 8-membered ring, and more preferably a 5- or 6-membered ring. The ring may also contain a heteroatom (e.g., a nitrogen atom, an oxygen atom, a sulfur atom, etc.) as a ring member. Furthermore, a carbon atom in the ring other than the carbon atoms (excluding the two carbon atoms specified in formula (1)) may be substituted with a carbonyl (>C=O) carbon atom.

[0073] When resin (A) contains a repeating unit represented by formula (1), the content of the repeating unit represented by formula (1) in resin (A) is preferably 5 to 95 mol %, more preferably 10 to 90 mol %, and even more preferably 20 to 80 mol %, based on the total repeating units of resin (A). Resin (A) may contain one type of repeating unit represented by formula (1), or two or more types. When two or more types are contained, it is preferable that the total content thereof be in the above range.

[0074] R in formula (2) ５ represents a hydrogen atom, a halogen atom or an organic group. ５ The organic group represented by the formula (I) is preferably an alkyl group or a cycloalkyl group. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. The alkyl group and the cycloalkyl group may have a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom or an iodine atom), a hydroxy group, a carboxyl group, an amino group, an amide group, an imide group, a thiol group, an acetyl group, a sulfonic acid group, a sulfonamide group, and an acetoxy group. R ５ The halogen atom represented by R is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom or a chlorine atom, and particularly preferably a chlorine atom. ５ As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, a methyl group or an ethyl group is particularly preferable, and a methyl group is most preferable.

[0075] R ６ and R ７The substituent represented by is not particularly limited, but is preferably an organic group, and more preferably an alkyl group or a cycloalkyl group. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably, for example, 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is, for example, preferably 3 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. R ６ and R ７ is preferably a hydrogen atom.

[0076] In formula (2), R ８ represents a substituent. ８ The substituent represented by is not particularly limited, and examples thereof include a group containing an onium salt structure, which will be described later, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a fluorinated alkyl group, a hydroxyl group, a carboxyl group, an acyl group, an acyloxy group, an alkoxy group, a carbamoyl group, a sulfonamide group, an amino group, a thiol group, and an alkylsulfonyl group. ８ If there are multiple R ８ may be the same or different, R ８ They may be bonded to each other to form a ring. ８ The ring formed by bonding together is not particularly limited and may be either a monocyclic ring or a polycyclic ring. The ring may contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member. The ring may also contain a carbonyl carbon as a ring member. The ring is preferably a 5- to 8-membered ring, and more preferably a 5- or 6-membered ring.

[0077] In formula (2), Ar １ represents a benzene ring group or a naphthalene ring group, and preferably represents a benzene ring group. In formula (2), k represents an integer of 0 to 7. １ When Ar represents a benzene ring group, k represents an integer of 0 to 5, and preferably an integer of 0 to 3. １When represents a naphthalene ring group, k represents an integer of 0 to 7, and preferably an integer of 0 to 3.

[0078] When resin (A) contains a repeating unit represented by formula (2), the content of the repeating unit represented by formula (2) in resin (A) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, and even more preferably 20 to 80 mol%, based on the total repeating units of resin (A). Resin (A) may contain one type of repeating unit represented by formula (2), or two or more types. When two or more types are contained, it is preferable that the total content thereof be in the above range.

[0079] (Group containing an onium salt structure) The group containing an onium salt structure will be described. The onium salt structure is a structural moiety having an ion pair of a cation and an anion, and is represented by "X ｎ－ nM ＋ " (where n represents, for example, an integer of 1 to 3, and preferably represents 1 or 2). M ＋ is a structural moiety containing a positively charged atom or atomic group, and X ｎ－ represents a structural moiety containing a negatively charged atom or atomic group. The anion in the onium salt structure is preferably a non-nucleophilic anion (an anion with extremely low ability to cause a nucleophilic reaction). When the anion in the onium salt structure is a non-nucleophilic anion, it is likely to become a photodegradable onium salt structure. The non-nucleophilic anion is the same as the non-nucleophilic anion in the onium salt described below.

[0080] Resin (A) can be synthesized by a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (A), as a polystyrene equivalent value measured by GPC, is preferably 1,000 or more, more preferably 2,500 or more, even more preferably 5,000 or more, particularly preferably 10,000 or more, and most preferably 20,000 or more. The weight average molecular weight of resin (A) is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less.

[0081] The polydispersity (molecular weight distribution, Mw / Mn) of the resin (A) is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The smaller the polydispersity, the better the resolution and resist shape.

[0082] When the resin (A) has two or more types of repeating units, it may be in the form of a random copolymer, a block copolymer, or an alternating copolymer.

[0083] The resin (A) may contain repeating units other than those described above. A preferred embodiment of the resin (A) is one in which the total content of the repeating units represented by formula (1) and the repeating units represented by formula (2) in the resin (A) is 70 mol % or more and 100 mol % or less, based on the total repeating units of the resin (A).

[0084] The content of resin (A) in composition (S1) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 65% ​​by mass or more, and particularly preferably 70% by mass or more, based on the total solid content of composition (S1). Furthermore, the content of resin (A) is 100% by mass or less, 95% by mass or less, or even 90% by mass or less, based on the total solid content of composition (S1). Resin (A) contained in composition (S1) may be one type or two or more types. In the case of two or more types, it is preferable that the total content thereof is within the above range.

[0085] (Solvent) The composition (S1) contains a solvent (also referred to as "solvent (B)"). The solvent (B) preferably contains (M1) a propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of a propylene glycol monoalkyl ether, a lactate ester, an acetate ester, an alkoxypropionate ester, a chain ketone, a cyclic ketone, a lactone, and an alkylene carbonate. The solvent (B) may further contain components other than the components (M1) and (M2).

[0086] As the component (M1), at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferred, and propylene glycol monomethyl ether acetate (PGMEA) is more preferred.

[0087] The following are preferred as component (M2). As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE) are preferred. As the lactate ester, ethyl lactate, butyl lactate, or propyl lactate is preferred. As the acetate ester, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferred. Butyl butyrate is also preferred. The alkoxypropionic acid ester is preferably methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP). The chain ketone is preferably 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone. The cyclic ketone is preferably methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone. The lactone is preferably γ-butyrolactone, and the alkylene carbonate is preferably propylene carbonate.

[0088] As component (M2), propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, methyl 2-hydroxyisobutyrate, γ-butyrolactone, or propylene carbonate is more preferred. Of these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is even more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.

[0089] In addition to the above-mentioned components, the solvent (B) also preferably contains an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and 2 or less heteroatoms. Preferred ester solvents having 7 or more carbon atoms and 2 or less heteroatoms are amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, or butyl butanoate, and more preferred isoamyl acetate.

[0090] Solvent (B) preferably contains component (M1). Solvent (B) more preferably consists essentially of component (M1) alone, or is a mixed solvent of component (M1) with other components. In the latter case, solvent (B) more preferably contains both component (M1) and component (M2). The mass ratio (M1 / M2) of component (M1) to component (M2) is preferably within the range of 100 / 0 to 15 / 85, more preferably within the range of 100 / 0 to 40 / 60, and even more preferably within the range of 100 / 0 to 60 / 40. In other words, solvent (B) preferably consists solely of component (M1) or contains both component (M1) and component (M2), and the mass ratio between them is as follows: That is, in the latter case, the mass ratio of component (M1) to component (M2) is preferably 15 / 85 or more, more preferably 40 / 60 or more, and even more preferably 60 / 40 or more.

[0091] When the solvent (B) contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) can be, for example, 99 / 1 or less.

[0092] When the solvent (B) further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0093] The content of the solvent (B) in the composition (S1) is preferably determined so that the solid content concentration of the composition (S1) is 0.5 to 30 mass%, and more preferably 1 to 20 mass%, in terms of better coatability.

[0094] The composition (S1) contains at least one of a compound represented by the following formula (1-m) and a compound represented by the following formula (2-m), and the total content of the compound represented by the following formula (1-m) and the compound represented by the following formula (2-m) in the composition (S1) may be 1 to 30,000 ppm by mass relative to the total mass of the composition (S1):

[0095]

[0096] In formula (1-m), R １ represents a halogen atom, a cyano group, an alkylsulfonyl group, an alkoxy group, a nitro group, an acyl group, an alkyl ester group, a halogenated alkyl group, or a halogenated cycloalkyl group. ２ and R ３ R each independently represents a hydrogen atom or a substituent. ４ represents a substituent. ２ or R ３ and R ４ may be bonded to form a ring.

[0097]

[0098] In formula (2-m), R ５ represents a hydrogen atom, a halogen atom or an organic group. ６ and R ７ Each independently represents a hydrogen atom or an organic group. １ represents a benzene ring group or a naphthalene ring group. ８represents a substituent. k represents an integer of 0 to 7. R ８ If there are multiple R ８ may be the same or different, and R ８ They may be bonded to each other to form a ring.

[0099] The compound represented by formula (1-m) may be a monomer corresponding to the repeating unit represented by formula (1). １ , R ２ , R ３ and R ４ The explanation, specific examples and preferred ranges of R in the above formula (1) are as follows: １ , R ２ , R ３ and R ４ The compound represented by formula (2-m) may be a monomer corresponding to the repeating unit represented by formula (2). ５ , R ６ , R ７ , R ８ , Ar １ The explanation, specific examples and preferred ranges of k and k are respectively based on R in the above formula (2). ５ , R ６ , R ７ , R ８ , Ar １ and k.

[0100] When the total content of the compound represented by formula (1-m) and the compound represented by formula (2-m) in composition (S1) is within the above range, these compounds (monomer components) are removed in step (X), and therefore the effects of the manufacturing method of the present invention are more easily exhibited. Composition (S2), which is the resist composition after step (X), may or may not contain at least one of the compound represented by formula (1-m) and the compound represented by formula (2-m). However, if it does contain them, the total content of the compound represented by formula (1-m) and the compound represented by formula (2-m) is preferably less than the total content of the compound represented by formula (1-m) and the compound represented by formula (2-m) in composition (S1), and is preferably less than 400 ppm by mass, more preferably less than 200 ppm by mass, even more preferably less than 100 ppm by mass, even more preferably less than 50 ppm by mass, particularly preferably less than 30 ppm by mass, and most preferably less than 15 ppm by mass, relative to the total mass of composition (S2).

[0101] The contents of the compound represented by formula (1-m) and the compound represented by formula (2-m) in the resist composition can be calculated by an area method in which peak area ratios are compared in chromatograms obtained by GPC measurement (Gel Permeation Chromatography (GPC) measurement using a GPC (Gel Permeation Chromatography) apparatus (Tosoh Corporation's HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: Tosoh Corporation's TSK gel Multipore HXL-M, column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector (Refractive Index Detector))). That is, by calculating the ratio of the area of ​​the peaks corresponding to the molecular weights of the compound represented by formula (1-m) and the compound represented by formula (2-m) to the total peak area of ​​the resist composition, the contents of the compound represented by formula (1-m) and the compound represented by formula (2-m) relative to the total mass of the mixture can be calculated.

[0102] (Ionic Compound (C)) The composition (S1) preferably further contains an ionic compound (C). The ionic compound (C) may be a compound that decomposes upon irradiation with actinic rays or radiation, or may be a compound that does not decompose. The compound that decomposes upon irradiation with actinic rays or radiation may be a compound that decomposes upon irradiation with actinic rays or radiation to generate an acid, or a compound that decomposes upon irradiation with actinic rays or radiation to generate a base. The ionic compound (C) is preferably a compound having an onium salt structure that decomposes upon irradiation with actinic rays or radiation to generate an acid (photodecomposable onium salt compound).

[0103] The photodegradable onium salt compound will now be described. The photodegradable onium salt compound preferably has at least one salt structural moiety composed of an anion moiety and a cation moiety, and decomposes upon exposure to generate an acid (preferably an organic acid). The salt structural moiety of the photodegradable onium salt compound is preferably composed of an organic cation moiety and an organic anion moiety with significantly low nucleophilicity, as these moieties are easily decomposed upon exposure and have excellent organic acid generation properties. The salt structural moiety may be a portion or the entirety of the photodegradable onium salt compound. An example of a case where the salt structural moiety is a portion of the photodegradable onium salt compound is a structure in which two or more salt structural moieties are linked, such as the photodegradable onium salt PG2 described below. The number of salt structural moieties in the photodegradable onium salt is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0104] Examples of organic acids generated from the photodegradable onium salt compound by the action of exposure include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimido acids, bis(alkylsulfonyl)imido acids, and tris(alkylsulfonyl)methide acids. Furthermore, the organic acid generated from the photodegradable onium salt compound by the action of exposure may be a polyvalent acid having two or more acid groups. For example, when the photodegradable onium salt compound is the photodegradable onium salt compound PG2 described below, the organic acid generated by decomposition of the photodegradable onium salt compound by exposure is a polyvalent acid having two or more acid groups.

[0105] In the photodecomposable onium salt compound, the cationic moiety constituting the salt structure moiety is preferably an organic cationic moiety, and among these, an organic cation represented by formula (ZaI) (cation (ZaI)) or an organic cation represented by formula (ZaII) (cation (ZaII)) described later is preferred.

[0106] (Photodecomposable Onium Salt Compound PG1) One example of a preferred embodiment of the photodecomposable onium salt compound is "M ＋ X － " which generates an organic acid upon exposure to light (hereinafter also referred to as "photodecomposable onium salt compound PG1"). ＋ X － In the compound represented by the formula ", M ＋ represents an organic cation, and X － represents an organic anion. The photodecomposable onium salt compound PG1 will be described below.

[0107] M in the photodecomposable onium salt compound PG1 ＋ The organic cation represented by formula (ZaI) (cation (ZaI)) or the organic cation represented by formula (ZaII) (cation (ZaII)) is preferred.

[0108]

[0109] In the above formula (ZaI), R ２０１ , R ２０２ , and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group represented by R is usually 1 to 30, and preferably 1 to 20. ２０１ ~R ２０３ Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are listed.

[0110] Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), an organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and an organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.

[0111] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ is an arylsulfonium cation, in which at least one of R is an aryl group. ２０１ ~R ２０３ may all be aryl groups, or R ２０１ ~R ２０３ A part of R may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ is an aryl group, and R ２０１ ~R ２０３ The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１~R ２０３ Examples of the group formed by combining two of the above include an alkylene group in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., a butylene group, a pentylene group, or a -CH ２ -CH ２ -O-CH ２ -CH ２ Examples of the arylsulfonium cation include triarylsulfonium cation, diarylalkylsulfonium cation, aryldialkylsulfonium cation, diarylcycloalkylsulfonium cation, and aryldicycloalkylsulfonium cation.

[0112] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group optionally contained in the arylsulfonium cation is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0113] R ２０１ ~R ２０３Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have are each independently an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom (e.g., fluorine, iodine), a hydroxy group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, a phenylthio group, etc. The above substituents may further have a substituent if possible, and for example, it is also preferred that the above alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.

[0114] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation represented by the formula (ZaI) R ２０１ ~R ２０３ are each independently a cation representing an organic group that does not have an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom. ２０１ ~R ２０３ The organic group having no aromatic ring as R generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. ２０１ ~R ２０３ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0115] R ２０１ ~R ２０３ Examples of the alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0116] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0117]

[0118] In formula (ZaI-3b), R １ｃ ~R ５ｃ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ R each independently represents a hydrogen atom, an alkyl group (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

[0119] R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0120] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of the group formed by bonding of R include alkylene groups such as butylene and pentylene. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0121] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ The ring formed by bonding together may have a substituent.

[0122] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0123]

[0124] In formula (ZaI-4b), l represents an integer of 0 to 2. r represents an integer of 0 to 8. １３represents a hydrogen atom, a halogen atom (for example, a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ represents a hydroxyl group, a halogen atom (for example, a fluorine atom, an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ When a plurality of R are present, each independently represents the above group such as a hydroxyl group. １５ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ may be bonded to each other to form a ring. １５ When two R are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. １５ are preferably alkylene groups and bonded to each other to form a ring structure. １５ The ring formed by bonding together may have a substituent.

[0125] In formula (ZaI-4b), R １３ , R １４ , and R １５ The alkyl group is preferably linear or branched, and the number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like.

[0126] Next, formula (ZaII) will be described. In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group.２０４ and R ２０５ The aryl group in R preferably has 2 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. ２０４ and R ２０５ The aryl group in R may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0127] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５ Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

[0128] Specific examples of the cation that can be contained in the compound (C1) are shown below, but the present invention is not limited to these.

[0129]

[0130]

[0131] X in the photodecomposable onium salt compound PG1 －The organic anion represented by the formula (I) is preferably a non-nucleophilic anion (an anion with extremely low ability to cause a nucleophilic reaction). Examples of the non-nucleophilic anion include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0132] The organic anion is preferably, for example, an organic anion represented by the following formula (DA).

[0133]

[0134] In formula (DA), A ３１ － represents an anionic group. ａ１ represents a hydrogen atom or a monovalent organic group. ａ１ represents a single bond or a divalent linking group. ３１ － and R ａ１ may be bonded to each other to form a ring.

[0135] A ３１ － represents an anionic group. ３１ － The anionic group represented by the formula (BA-1) is not particularly limited, but is preferably a group selected from the group consisting of groups represented by formulas (BA-1) to (BA-13), more preferably formula (BA-1), formula (BA-2), formula (BA-3), formula (BA-4), formula (BA-5), formula (BA-6), formula (BA-10), formula (BA-11), formula (BA-12), and formula (BA-13), and particularly preferably formula (BA-4), formula (BA-6), and formula (BA-12).

[0136]

[0137] In formulae (BA-1) to (BA-13), * represents a bonding position. In formulae (BA-1) to (BA-5) and formula (BA-10), R Ｘ１Each independently represents a monovalent organic group. Ｘ２ Each of the two R in formula (BA-7) independently represents a hydrogen atom or a substituent other than a fluorine atom or a perfluoroalkyl group. Ｘ２ may be the same or different. Ｘ３ represents a hydrogen atom, a halogen atom, or a monovalent organic group. n1 represents an integer of 0 to 4. When n1 represents an integer of 2 to 4, a plurality of R Ｘ３ may be the same or different. The group that bonds to the bonding position represented by * in Formula (BA-12) and Formula (BA-13) is preferably an alkylene group or an arylene group, more preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and particularly preferably a phenylene group. The alkylene group and the arylene group may have a substituent, which is not particularly limited and includes, for example, a halogen atom.

[0138] In formulas (BA-1) to (BA-5) and formula (BA-10), R Ｘ１ R each independently represents a monovalent organic group. Ｘ１ As the R, an alkyl group (which may be linear or branched, and preferably has 1 to 15 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms), or an aryl group (which may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms) is preferred. Ｘ１ The above group represented by the formula (B-5) may have a substituent. Ｘ１ The atom directly bonded to N- in -CO- and -SO ２ It is also preferred that neither of the sulfur atoms in - is present.

[0139] R Ｘ１ The cycloalkyl group in R may be monocyclic or polycyclic. Ｘ１ Examples of the cycloalkyl group in the formula include a norbornyl group and an adamantyl group.

[0140] R Ｘ１The substituent that the cycloalkyl group in R may have is not particularly limited, but is preferably an alkyl group (which may be linear or branched, and preferably has 1 to 5 carbon atoms). Ｘ１ One or more of the carbon atoms which are ring members of the cycloalkyl group in the formula (I) may be replaced by a carbonyl carbon atom.

[0141] R Ｘ１ The alkyl group in R preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Ｘ１ The substituent that the alkyl group in R may have is not particularly limited, but is preferably, for example, a cycloalkyl group, a fluorine atom, or a cyano group. Examples of the cycloalkyl group as the substituent include R Ｘ１ is the same as the cycloalkyl group described above when R Ｘ１ When the alkyl group in R has a fluorine atom as the substituent, the alkyl group may be a perfluoroalkyl group. Ｘ１ The alkyl group in ２ - may be substituted with a carbonyl group.

[0142] R Ｘ１ The aryl group in R is preferably a phenyl group. Ｘ１ The substituent that the aryl group in R may have is not particularly limited, but is preferably an alkyl group, a fluorine atom, or a cyano group. Ｘ１ is the same as the alkyl group described above when it is an alkyl group.

[0143] In formulas (BA-7) and (BA-9), R Ｘ２ each independently represents a hydrogen atom or a substituent other than a fluorine atom or a perfluoroalkyl group (for example, an alkyl group not containing a fluorine atom and a cycloalkyl group not containing a fluorine atom). Ｘ２ may be the same or different.

[0144] In formula (BA-8), R Ｘ３ represents a hydrogen atom, a halogen atom, or a monovalent organic group.Ｘ３ Examples of the halogen atom as R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Ｘ３ The monovalent organic group as R Ｘ１ n1 represents an integer of 0 to 4. n1 is preferably an integer of 0 to 2, and more preferably 0 or 1. When n1 represents an integer of 2 to 4, a plurality of R Ｘ３ may be the same or different.

[0145] In formula (DA), R ａ１ The number of carbon atoms in the monovalent organic group is not particularly limited, but is preferably 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. ａ１ is preferably an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms. The aryl group may be monocyclic or polycyclic, and is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. The cycloalkyl group may contain a heteroatom as a ring member atom. Examples of heteroatoms include, but are not limited to, a nitrogen atom and an oxygen atom. The cycloalkyl group may also contain a carbonyl bond (>C═O) as a ring member atom. The alkyl group, cycloalkyl group, and aryl group may further have a substituent. Furthermore, A ３１ － and R ａ１ may be bonded to each other to form a ring.

[0146] L ａ１The divalent linking group as is not particularly limited, and examples thereof include an alkylene group, a cycloalkylene group, an aromatic group, -O-, -CO-, -COO-, and a group formed by combining two or more of these. The alkylene group may be linear or branched and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The cycloalkylene group may be monocyclic or polycyclic and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms. The aromatic group is a divalent aromatic group, and preferably has 6 to 20 carbon atoms, more preferably has 6 to 15 carbon atoms. The aromatic ring constituting the aromatic group may be an aromatic hydrocarbon ring or an aromatic heterocycle. The aromatic ring is not particularly limited, and examples thereof include aromatic rings having 6 to 20 carbon atoms, and specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a thiophene ring. The aromatic ring constituting the aromatic group is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The alkylene group, the cycloalkylene group, and the aromatic group may further have a substituent, and the substituent is preferably a halogen atom. ａ１ preferably represents a single bond.

[0147] As the photodecomposable onium salt compound PG1, it is also preferable to use, for example, the photoacid generators disclosed in paragraphs

[0135] to

[0171] of WO 2018 / 193954, paragraphs

[0077] to

[0116] of WO 2020 / 066824, and paragraphs

[0018] to

[0075] and

[0334] to

[0335] of WO 2017 / 154345.

[0148] The molecular weight of the photodecomposable onium salt compound PG1 is not particularly limited, but is preferably not more than 3000, more preferably not more than 2000, and even more preferably not more than 1000. The molecular weight of the photodecomposable onium salt compound PG1 may be 100 or more.

[0149] (Photodecomposable onium salt compound PG2) Another example of a suitable embodiment of the photodecomposable onium salt compound includes the following compound (I) and compound (II) (hereinafter, "compound (I) and compound (II)" will also be referred to as "photodecomposable onium salt compound PG2"). The photodecomposable onium salt compound PG2 has two or more of the above-mentioned salt structural moieties and generates a polyvalent organic acid upon exposure to light. The photodecomposable onium salt compound PG2 will be described below.

[0150] Compound (I) Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing a first acidic moiety derived from the structural moiety X and a second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation: Structural moiety X: Anionic moiety A １ － and the cationic moiety M １ ＋ and HA is produced by irradiation with actinic rays or radiation. １ Structural moiety Y: anionic moiety A, which forms a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋ and HA is produced by irradiation with actinic rays or radiation. ２ A structural moiety forming a second acidic moiety represented by the following formula (I):

[0151] Condition I: In the compound (I), the cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cation moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by２ The compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.

[0152] When compound (I) has two or more structural moieties X, the structural moieties X may be the same or different from each other. １ － , and two or more of the above M １ ＋ may be the same or different. １ － and the above A ２ － , and the above M １ ＋ and the above M ２ ＋ may be the same or different, but １ － and the above A ２ － are preferably different from each other.

[0153] Anion site A １ － and anionic moiety A ２ － is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. In the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. Ａ represents a monovalent organic group. Ａ Examples of the monovalent organic group represented by the formula (I) include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0154]

[0155]

[0156] In addition, the cationic moiety M １ ＋and cationic moiety M ２ ＋ is a structural moiety containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. The organic cation is not particularly limited, but is preferably an organic cation represented by the above formula (ZaI) (cation (ZaI)) or an organic cation represented by the above formula (ZaII) (cation (ZaII)).

[0157] Compound (II) Compound (II) is a compound having two or more of the structural moieties X and one or more of the structural moieties Z described below, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z upon irradiation with actinic rays or radiation. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

[0158] The compound (II) can be converted into the cation moiety M in the structural moiety X by irradiation with actinic rays or radiation. １ ＋ H ＋ HA is replaced by １ In other words, the compound PII can generate a compound PII (acid) having an acidic site represented by the above HA. １ and a structural moiety Z, which is a nonionic moiety capable of neutralizing the acid. In compound (II), the definition of the structural moiety X and A １ － and M １ ＋ The definition of the structural moiety X in the compound (I) and the definition of A １ － and M １ ＋ The definition and preferred embodiments are the same as those of the above. In addition, the two or more structural moieties X may be the same or different. In addition, the two or more structural moieties A １ － , and two or more of the above M １ ＋ may be the same or different.

[0159] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a functional group having an electron or a group capable of electrostatically interacting with a proton. Examples of the functional group having an electron or a group capable of electrostatically interacting with a proton include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0160]

[0161] Examples of the partial structure of the functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Of these, a primary amine structure, a secondary amine structure, a tertiary amine structure, and a tertiary amine structure are preferred.

[0162] The molecular weight of the photodegradable onium salt compound PG2 is preferably 100 to 10,000, more preferably 100 to 2,500, and even more preferably 100 to 1,500.

[0163] Examples of the photodecomposable onium salt compound PG2 include the compounds exemplified in paragraphs

[0023] to

[0095] of WO 2020 / 158313.

[0164] When the composition (S1) contains an ionic compound (C), the content of the ionic compound (C) in the composition (S1) is not particularly limited, but is preferably 0.25% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total solid content of the composition (S1). The content of the ionic compound (C) 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, based on the total solid content of the composition (S1).

[0165] (Other Components) The composition (S1) may contain other components in addition to the above-described components. The other components are not particularly limited, but examples thereof include a hydrophobic resin and a surfactant.

[0166] <Hydrophobic Resin> The composition (S1) may further contain a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in the molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances. The effects of adding a hydrophobic resin include controlling the static and dynamic contact angles of the resist film surface with the developer and suppressing outgassing.

[0167] The hydrophobic resin contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３ It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0168] When composition (S1) contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass% and more preferably 0.1 to 15.0 mass% based on the total solid content of composition (S1). One type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0169] <Surfactant> The composition (S1) may contain a surfactant. When a surfactant is contained, the adhesion is improved and a pattern with fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954. When the composition (S1) contains a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass%, more preferably 0.0005 to 1 mass%, based on the total solid content of the composition (S1). One type of surfactant may be used, or two or more types may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0170] [Composition (S2)] The description of composition (S2), which is the actinic ray- or radiation-sensitive resin composition (resist composition) after step (X) in the production method of the present invention, is the same as that of composition (S1) described above, except for the total content of the compound represented by formula (1-m) and the compound represented by formula (2-m) described above. However, when the gelling component in composition (S1) is removed by performing step (X), the Mw and Mn of resin (A) in composition (S2) tend to be smaller than the Mw and Mn of resin (A) in composition (S1), and the solids concentration in composition (S2) tends to be lower than the solids concentration in composition (S1).

[0171] [Pattern Forming Method] The pattern forming method of the present invention is a pattern forming method comprising the steps of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition (resist composition) produced by the production method of the present invention described above (also referred to as "Step 1"), exposing the resist film to light (also referred to as "Step 2"), and developing the exposed resist film using a developer (also referred to as "Step 3").

[0172] <Step 1: Resist Film Forming Step> Step 1 is a step of forming a resist film on a substrate using a resist composition.

[0173] An example of a method for forming a resist film on a substrate using a resist composition is a method in which the resist composition is applied onto the substrate.

[0174] The resist composition can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide) such as those used in the manufacture of integrated circuit elements by an appropriate application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed when spin application using a spinner is preferably 1000 to 3000 rpm (rotations per minute). After application of the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed below the resist film.

[0175] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or developing machine, and may also be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0176] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming a finer pattern with higher precision. In particular, when EUV exposure and EB exposure are used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. Furthermore, when ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0177] A top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be uniformly applied to the resist film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of JP 2014-059543 A. For example, a top coat containing a basic compound such as that described in JP 2013-061648 A is preferably formed on the resist film. It is also preferable that the top coat contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0178] <Step 2: Exposure Step> Step 2 is a step of exposing the resist film. Examples of exposure methods include irradiating the formed resist film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, and preferably far ultraviolet light with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Examples include excimer laser (157 nm), EUV (13 nm), X-ray, and electron beam.

[0179] After exposure, it is preferable to perform post-exposure heat treatment (also referred to as post-exposure baking) before development. Post-exposure heat treatment promotes the reaction of the exposed area, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like.

[0180] <Step 3: Development Step> Step 3 is a step of developing the exposed resist film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer), but an organic developer is preferred.

[0181] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of a substrate by surface tension and then left stationary for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispense nozzle is scanned at a constant speed (dynamic dispense method). After the development step, a step of stopping development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0182] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include aqueous alkaline solutions containing a quaternary ammonium salt, such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0183] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0184] The above-mentioned solvents may be mixed in plural, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0185] <Other Steps> The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0186] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse liquid.

[0187] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0188] The method for the rinsing step is not particularly limited, and examples include a method in which a rinsing solution is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinsing solution for a certain period of time (dipping method), and a method in which the rinsing solution is sprayed onto the surface of the substrate (spray method). The pattern formation method of the present invention may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern by baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0189] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferred. The dry etching is preferably oxygen plasma etching.

[0190] The resist composition and various materials used in the pattern formation method of the present invention (e.g., solvent, developer, rinse, anti-reflective coating composition, top coat composition, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0191] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0192] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0193] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less.

[0194] The resist composition may also contain water as an impurity. When water is contained as an impurity, the lower the content of water, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water relative to the total solid content of the resist composition. The resist composition may also contain residual monomers as impurities (for example, monomers derived from the raw material monomers used in the synthesis of the resin (A)). When water is contained as an impurity, the lower the content of residual monomers, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water relative to the total solid content of the resist composition.

[0195] A conductive compound may be added to an organic processing liquid such as a rinse solution to prevent breakdown of the chemical solution piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less. For the chemical solution piping, for example, stainless steel (SUS), or various piping coated with antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used. Similarly, for the filters and O-rings, polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin) that have been antistatically treated can be used.

[0196] [Method for Manufacturing Electronic Device] The present invention also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. The electronic device of the present invention is suitable for installation in electrical and electronic equipment (such as home appliances, office automation (OA), media-related equipment, optical equipment, and communication equipment).

[0197] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0198] [Various Components of Actinic Ray- or Radiation-Sensitive Resin Composition (Resist Composition)] [Resin (A)] Resins (A-1 to A-10) shown in Table 1 were used as resin (A). Table 1 shows the content (mol %; corresponding in order from left to right), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit shown below. The weight average molecular weight (Mw) and dispersity (Mw / Mn) were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The content of each repeating unit was １３ Measurement was performed by C-NMR (Nuclear Magnetic Resonance).

[0199]

[0200] The structural formulae of A-1 to A-10 are shown below.

[0201]

[0202] [Solvent] The solvents used are shown in Table 2 below.

[0203]

[0204] [Ionic Compound] The structural formula of the ionic compound C-1 used is shown below: C-1 is a photodecomposable onium salt compound.

[0205]

[0206] [Preparation of Resist Compositions] Resist compositions Re-1 to Re-11 were obtained by mixing the components other than the solvent shown in Table 3 below in the amounts (% by mass) shown in Table 3 with the solvent shown in Table 3. The amount of each component is the mass ratio (% by mass) to the total solid content of the resist composition. When two or more compounds were used as components, they were separated by " / ". The order of the types and amounts separated by " / " corresponds to each other. The solid content concentration of each resist composition was adjusted to 1.6% by mass. The solid content refers to all components other than the solvent. Table 3 lists the types of solvents used and their mixing ratios (% by mass). The resulting resist composition was used as composition (S1) in the examples and comparative examples.

[0207]

[0208] In Re-6, the mixing ratio of B-1 and B-7 was 80 / 20 by mass.

[0209] Examples 1 to 22, Comparative Examples 1 to 3 [Filter Filtration] Composition (S1) shown in Table 4 below was passed through the filter shown in Table 4 and filtered to produce composition (S2) shown in Table 4. Specifically, a filtration device was used in which a first filter, a second filter, a third filter, and a fourth filter were arranged in this order on the filtration flow path. However, the second filter, the third filter, and the fourth filter were used only when noted in Table 4. The filtration method was one of multistage filtration, circulating filtration, and multi-pass filtration. In Table 4, "multistage" indicates that multistage filtration was performed, "circulating" indicates that circulating filtration was performed, and "multiple-pass" indicates that multi-pass filtration was performed. Table 4 also lists the "number of passes," which indicates how many times the resist composition passed through each filter. For example, in the "filtration method, number of passes" column of Example 1, "multistage, one pass" means that the resist composition was subjected to multistage filtration, passing once through the first filter and once through the second filter. The term "two circulations" in Example 9 refers to a case in which the resist composition passed through each of the first, second, and third filters once, and then returned to the primary side of the first filter, where it was again subjected to circulating filtration by passing through each of the first, second, and third filters once each (i.e., passing through each filter twice). The term "single multiple pass" in Example 15 refers to a case in which the resist composition passed through each of the first, second, and third filters once, and then removed and introduced into a filtration device in which the same type of first, second, and third filters, but from different lots, were arranged on the filtration flow path, where it was subjected to multiple pass filtration by passing through each of the first, second, and third filters once each. The filter types were indicated by their pore size and material (the material constituting the filters). Regarding materials, "Nylon" refers to nylon 66, "PE" refers to polyethylene, "PP" refers to polypropylene, "PI" refers to polyimide, and "PTFE" refers to polytetrafluoroethylene. For example, "10 nm Nylon" refers to a nylon 66 filter with a pore size of 10 nm.

[0210] [Measurement of the Content of Residual Monomer Component in Resist Composition] The content of the residual monomer component (the monomer component used in the synthesis of Resin (A)) in the resist compositions (Composition (S1) and Composition (S2)) was measured. Specifically, the content was calculated by an area method in which peak area ratios were compared in chromatograms obtained by GPC measurement (Gel Permeation Chromatography (GPC) measurement using a GPC (Gel Permeation Chromatography) apparatus (Tosoh Corporation, HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: Tosoh Corporation, TSK gel Multipore HXL-M, column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector). That is, the content of the monomer component relative to the total mass of the resist compositions (compositions (S1) and (S2)) was calculated by taking the ratio of the area of ​​the peak corresponding to the molecular weight of the monomer component to the total peak area of ​​the resist compositions (compositions (S1) and (S2)). The results are shown in Table 4 below. In Table 4, "RM1" represents the content (unit: ppm by mass) of the remaining monomer component relative to the total mass of composition (S1), and "RM2" represents the content (unit: ppm by mass) of the remaining monomer component relative to the total mass of composition (S2). It should be noted that even for the same type of resist composition (composition (S1)), the content of the remaining monomer component may vary from experiment to experiment.

[0211] [Pattern Formation] An underlayer film-forming composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A composition (S2) shown in Table 4 was applied to the underlayer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. This resulted in a silicon wafer with a resist film. The silicon wafer with the resist film obtained by the above procedure was subjected to pattern exposure using an EUV exposure device (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask with a line width of 20 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90° C. for 60 seconds, then developed for 30 seconds with the developer shown in Table 4, and spin-dried to obtain a pattern.

[0212]

[0213] [Developer] The developers used are shown in Table 5 below.

[0214]

[0215] [Evaluation] <LWR> The optimum exposure dose when resolving a line and space pattern with a line width of 20 nm (1:1) using a critical dimension scanning electron microscope (Hitachi, Ltd. S-9380II) was determined as sensitivity (Eopt) (mJ / cm ２ A line and space pattern (resist pattern) with a line width of 20 nm (1:1) resolved at an exposure dose indicating the sensitivity (Eopt) was observed from above the pattern using a critical dimension scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)). The line width of the pattern was observed at an arbitrary point, and its standard deviation (σ １ ) and σ １ 3σ, which is three times the value of １The composition (S1) used in each of the Examples and Comparative Examples was passed through a polyethylene filter having a pore size of 0.1 μm once to form a resist composition. The resist composition was then filtered using the same method as in the above-mentioned [Pattern formation]. The pattern line width was observed at an arbitrary point, and its standard deviation (σ ０ ) and σ ０ 3σ, which is three times the value of ０ was calculated. １ / 3σ ０ (3σ １ 3σ ０ The evaluation was carried out as follows: if the 3σ was less than 0.88, S if it was 0.88 or more and less than 0.91, A if it was 0.91 or more and less than 0.94, B if it was 0.94 or more and less than 0.96, C if it was 0.96 or more and less than 0.99, D if it was 0.96 or more and less than 0.99, and E if it was 0.99 or more. The results are shown in the "LWR" column in Table 4. １ / 3σ ０ The smaller the value, the better the LWR performance.

[0216] The results in Table 4 show that the resist composition (composition (S2)) produced by the method of the example has excellent LWR performance.

[0217] According to the present invention, there is provided a method for producing an actinic ray-sensitive or radiation-sensitive resin composition having excellent LWR performance. Furthermore, according to the present invention, there is provided a pattern formation method and a method for producing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

[0218] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-141461) filed on August 31, 2023, the contents of which are incorporated herein by reference.

[0219] 10 Purification device 11 Tank 12(a), 12(b) Filter unit 13 Filling device 14 Pipe 15(a) Regulating valve 16 Filtration device

Claims

1. A method for producing an actinic ray-sensitive or radiation-sensitive resin composition, comprising a step (X) of filtering an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) whose main chain is decomposed by irradiation with actinic rays or radiation and a solvent through two or more types of filters.

2. A method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) contains at least one of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): In formula (1), R １ R represents a halogen atom, a cyano group, an alkylsulfonyl group, an alkoxy group, a nitro group, an acyl group, an alkyl ester group, a halogenated alkyl group, or a halogenated cycloalkyl group. ２ and R ３ Each independently represents a hydrogen atom or a substituent. ４ represents a substituent. ２ Or R ３ and R ４ may be bonded to form a ring. In formula (2), R ５ represents a hydrogen atom, a halogen atom or an organic group. ６ and R ７ Each independently represents a hydrogen atom or an organic group. １ represents a benzene ring group or a naphthalene ring group. ８ represents a substituent. k represents an integer of 0 to 7. ８ When there are multiple R ８ may be the same or different, R ８ They may be bonded to each other to form a ring.

3. The method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the resin (A) contains a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2).

4. The method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the actinic ray-sensitive or radiation-sensitive resin composition before being filtered in step (X) contains at least one of a compound represented by the following formula (1-m) and a compound represented by the following formula (2-m), and the total content of the compound represented by the following formula (1-m) and the compound represented by the following formula (2-m) in the actinic ray-sensitive or radiation-sensitive resin composition before being filtered in step (X) is 1 to 30,000 ppm by mass with respect to the total mass of the composition. In formula (1-m), R １ R represents a halogen atom, a cyano group, an alkylsulfonyl group, an alkoxy group, a nitro group, an acyl group, an alkyl ester group, a halogenated alkyl group, or a halogenated cycloalkyl group. ２ and R ３ Each independently represents a hydrogen atom or a substituent. ４ represents a substituent. ２ Or R ３ and R ４ may be bonded to form a ring. In formula (2-m), R ５ represents a hydrogen atom, a halogen atom or an organic group. ６ and R ７ Each independently represents a hydrogen atom or an organic group. １ represents a benzene ring group or a naphthalene ring group. ８ represents a substituent. k represents an integer of 0 to 7. ８ When there are multiple R ８ may be the same or different, R ８ They may be bonded to each other to form a ring.

5. A method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the weight average molecular weight of the resin (A) in the actinic ray-sensitive or radiation-sensitive resin composition before filtering in step (X) is 20,000 or more.

6. A method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein at least two of the filters have different pore sizes, and a filter having a relatively large pore size and a filter having a relatively small pore size are arranged in this order on the filtration flow path.

7. The method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the pore size of the first filter disposed on the filtration flow path among the filters is 20 nm or less.

8. The method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the pore size of the first filter disposed on the filtration flow path among the filters is 5 nm or more.

9. The method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the pore size of the filters arranged second or subsequent to the filter arranged on the filtration flow path is 5 nm or less.

10. A method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the step (X) includes a step of circulating the actinic ray-sensitive or radiation-sensitive resin composition that has passed through the filter and passing it through the same filter again.

11. A pattern forming method comprising the steps of forming a resist film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition produced by the method according to any one of claims 1 to 10, exposing the resist film to light, and developing the exposed resist film with a developer.

12. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 11.

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